Benchmark Density Functional Theory Approach for the Calculation of Bond Dissociation Energies of the M–O₂ Bond: A Key Step in Water Splitting Reactions

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This article references 55 other publications.

1. 1

   Shahbaz, M.; Mutascu, M.; Azim, P. Environmental Kuznets Curve in Romania and the Role of Energy Consumption. Renewable Sustainable Energy Rev. 2013, 18, 165– 173,  DOI: 10.1016/j.rser.2012.10.012

   Google Scholar

   There is no corresponding record for this reference.
2. 2

   Bard, A. J.; Fox, M. A. Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen. Acc. Chem. Res. 1995, 28, 141– 145,  DOI: 10.1021/ar00051a007

   Google Scholar

   2

   Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen

   Bard, Allen J.; Fox, Marye Anne

   Accounts of Chemical Research (1995), 28 (3), 141-5CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)

   A review with 33 refs. of history and progress of water splitting, semiconductor solid state photovoltaic based systems, semiconductor electrode liq. junction systems, semiconductor particle systems, sensitized semiconductor systems, homogeneous and microheterogeneous systems, and future prospects.

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3. 3

   Chow, J.; Kopp, R. J.; Portney, P. R. Energy Resources and Global Development. Science 2003, 302, 1528– 1531,  DOI: 10.1126/science.1091939

   Google Scholar

   3

   Energy resources and global development

   Chow Jeffrey; Kopp Raymond J; Portney Paul R

   Science (New York, N.Y.) (2003), 302 (5650), 1528-31 ISSN:.

   In order to address the economic and environmental consequences of our global energy system, we consider the availability and consumption of energy resources. Problems arise from our dependence on combustible fuels, the environmental risks associated with their extraction, and the environmental damage caused by their emissions. Yet no primary energy source, be it renewable or nonrenewable, is free of environmental or economic limitations. As developed and developing economies continue to grow, conversion to and adoption of environmentally benign energy technology will depend on political and economic realities.

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4. 4

   Navarro Yerga, R. M.; Álvarez Galván, M. C.; del Valle, F.; Villoria de la Mano, J. A.; Fierro, J. L. G. Water Splitting on Semiconductor Catalysts under Visible-Light Irradiation. ChemSusChem 2009, 2, 471– 485,  DOI: 10.1002/cssc.200900018

   Google Scholar

   4

   Water Splitting on Semiconductor Catalysts under Visible-Light Irradiation

   Navarro Yerga, Rufino M.; Alvarez Galvan, M. Consuelo; del Valle, F.; Villoria de la Mano, Jose A.; Fierro, Jose L. G.

   ChemSusChem (2009), 2 (6), 471-485CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)

   A review. The conversion of solar energy into hydrogen via the water-splitting process, assisted by photo-semiconductor catalysts, is one of the most promising technologies for the future because large quantities of hydrogen can potentially be generated in a clean and sustainable manner. This paper provides an overview of the principles, approaches, and research progress on solar hydrogen prodn. via the water-splitting reaction on photo-semiconductor catalysts. It presents a survey of the advances made over the last decades in the development of catalysts for photochem. water splitting under visible-light irradn. The paper also analyzes the energy requirements and main factors that det. the activity of photocatalysts in the conversion of water into hydrogen and oxygen using sunlight. Remarkable progress has been made since the pioneering work by Fujishima and Honda in 1972, but his development of photocatalysts with improved efficiencies for hydrogen prodn. from water using solar energy still faces major challenges. Research strategies and approaches adopted in the search for active and efficient photocatalysts, for example through new materials and synthesis methods, are presented and analyzed.

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5. 5

   Barton, E. E.; Rampulla, D. M.; Bocarsly, A. B. Selective Solar-Driven Reduction of CO 2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell. J. Am. Chem. Soc. 2008, 130, 6342– 6344,  DOI: 10.1021/ja0776327

   Google Scholar

   5

   Selective Solar-Driven Reduction of CO2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell

   Barton, Emily E.; Rampulla, David M.; Bocarsly, Andrew B.

   Journal of the American Chemical Society (2008), 130 (20), 6342-6344CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

   With rising atm. CO2 levels there is interest in artificial photosynthetic schemes for converting this greenhouse gas into fuel and small orgs. Photoelectrochem. schemes for activating the inert CO2 mol. operate at high overpotentials and thus do not convert light energy to chem. energy. A selective conversion of CO2 to MeOH at a p-GaP semiconductor electrode with a homogeneous pyridinium ion catalyst, driving the reaction with light energy to yield faradaic efficiencies near 100% at potentials well below the std. potential, is described.

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6. 6

   Rashatasakhon, P.; Ozdemir, A. D.; Willis, J.; Padwa, A. Six- versus Five-Membered Ring Formation in Radical Cyclizations of 7-Bromo-Substituted Hexahydroindolinones. Org. Lett. 2004, 6, 917– 920,  DOI: 10.1021/ol036347z

   Google Scholar

   6

   Six- versus Five-Membered Ring Formation in Radical Cyclizations of 7-Bromo-Substituted Hexahydroindolinones

   Rashatasakhon, Paitoon; Ozdemir, Ayse Daut; Willis, Jerremey; Padwa, Albert

   Organic Letters (2004), 6 (6), 917-920CODEN: ORLEF7; ISSN:1523-7060. (American Chemical Society)

   Radical cyclization of N-allyl-7-bromo-3a-methyl-hexahydroindol-2-one affords a six-membered ring product that prevails over the isomeric five-membered compd. The former product is generated through two reaction pathways: (a) 6-endo-trig ring closure and (b) rearrangement of an intermediate methylenecyclopentyl radical obtained by 5-exo-trig cyclization.

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7. 7

   Service, R. F. Turning Over a New Leaf. Science 2011, 334, 925– 927,  DOI: 10.1126/science.334.6058.925

   Google Scholar

   7

   Turning over a new leaf

   Service, Robert F.

   Science (Washington, DC, United States) (2011), 334 (6058), 925-927CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)

   There is no expanded citation for this reference.

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8. 8

   Kurz, P.; Berggren, G.; Anderlund, M. F.; Styring, S. Oxygen Evolving Reactions Catalysed by Synthetic Manganese Complexes: A Systematic Screening. Dalton Trans. 2007, 38, 4258,  DOI: 10.1039/b710761g

   Google Scholar

   There is no corresponding record for this reference.
9. 9

   Zong, R.; Thummel, R. P. A New Family of Ru Complexes for Water Oxidation. J. Am. Chem. Soc. 2005, 127, 12802– 12803,  DOI: 10.1021/ja054791m

   Google Scholar

   9

   A New Family of Ru Complexes for Water Oxidation

   Zong, Ruifa; Thummel, Randolph P.

   Journal of the American Chemical Society (2005), 127 (37), 12802-12803CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

   Reaction of the bridging ligand 3,6-bis-[6'-(1'',8''-naphthyrid-2''-yl)-pyrid-2'-yl]pyridazine (1) with [Ru(DMSO)4Cl2] in aq. ethanol followed by excess 4-substituted pyridine (4-R-py) in the presence of triethylamine provides a series of three well-organized dinuclear complexes characterized by 1H NMR, MS, and X-ray. Mononuclear analogs are prepd. from 4-tert-butyl-2,6-di(1',8'-naphthyrid-2'-yl)pyridine (5) and characterized in a similar fashion. All six complexes show electronic absorption and redox properties consistent with the electron donor/acceptor ability of the axial 4-R-py ligand. When an acetonitrile soln. of the catalyst is added to an aq. Ce(IV)-CF3SO3H soln. (pH = 1.0) at 24 °C, oxygen evolution is obsd. for both mono and dinuclear systems. Turnover nos. range from 50 to 3200 with the best results being found when the axial ligand is 4-methylpyridine (mononuclear TN = 580 and dinuclear TN = 3200).

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10. 10

    Polyansky, D. E.; Muckerman, J. T.; Rochford, J.; Zong, R.; Thummel, R. P.; Fujita, E. Water Oxidation by a Mononuclear Ruthenium Catalyst: Characterization of the Intermediates. J. Am. Chem. Soc. 2011, 133, 14649– 14665,  DOI: 10.1021/ja203249e

    Google Scholar

    10

    Water Oxidation by a Mononuclear Ruthenium Catalyst: Characterization of the Intermediates

    Polyansky, Dmitry E.; Muckerman, James T.; Rochford, Jonathan; Zong, Ruifa; Thummel, Randolph P.; Fujita, Etsuko

    Journal of the American Chemical Society (2011), 133 (37), 14649-14665CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    A detailed characterization of intermediates in water oxidn. catalyzed by a mononuclear Ru polypyridyl complex [RuII-OH2]2+ (Ru = Ru complex with one 4-t-butyl-2,6-di-(1',8'-naphthyrid-2'-yl)-pyridine ligand and two 4-picoline ligands) has been carried out using electrochem., UV-vis and resonance Raman spectroscopy, pulse radiolysis, stopped flow, and electrospray ionization mass spectrometry (ESI-MS) with H218O labeling expts. and theor. calcns. The results reveal a no. of intriguing properties of intermediates such as [RuIV=O]2+ and [RuIV-OO]2+. At pH > 2.9, two consecutive proton-coupled one-electron steps take place at the potential of the [RuIII-OH]2+/[RuII-OH2]2+ couple, which is equal to or higher than the potential of the [RuIV=O]2+/[RuIII-OH]2+ couple (i.e., the observation of a two-electron oxidn. in cyclic voltammetry). At pH 1, the rate const. of the first one-electron oxidn. by Ce(IV) is k1 = 2 × 104 M-1 s-1. While pH-independent oxidn. of [RuIV=O]2+ takes place at 1420 mV vs NHE, bulk electrolysis of [RuII-OH2]2+ at 1260 mV vs NHE at pH 1 (0.1 M triflic acid) and 1150 mV at pH 6 (10 mM sodium phosphate) yielded a red colored soln. with a Coulomb count corresponding to a net four-electron oxidn. ESI-MS with labeling expts. clearly indicates that this species has an O-O bond. This species required an addnl. oxidn. to liberate an oxygen mol., and without any addnl. oxidant it completely decompd. slowly to form [RuII-OOH]+ over 2 wk. While there remains some conflicting evidence, we have assigned this species as 1[RuIV-η2-OO]2+ based on our electrochem., spectroscopic, and theor. observations alongside a previously reported anal.

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11. 11

    Baran, J. D.; Grönbeck, H.; Hellman, A. Analysis of Porphyrines as Catalysts for Electrochemical Reduction of O 2 and Oxidation of H 2 O. J. Am. Chem. Soc. 2014, 136, 1320– 1326,  DOI: 10.1021/ja4060299

    Google Scholar

    11

    Analysis of Porphyrins as Catalysts for Electrochemical Reduction of O2 and Oxidation of H2O

    Baran, Jakub D.; Groenbeck, Henrik; Hellman, Anders

    Journal of the American Chemical Society (2014), 136 (4), 1320-1326CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    Bioinspired structures are promising as improved catalysts for various redox reactions. One example is metal hangman-porphyrins (MHP), which recently were suggested for O redn./evolution reaction (ORR/OER). The unique properties of the MHPs are attributed to both the hangman scaffold and the C6F5 side groups. Herein, the OER/ORR over various transition metal MHPs was studied by d. functional theory calcns. within an electrochem. framework. A comparison of the reaction landscape for MHP, metal porphyrins (MP) and metal tetrafluorophenyloporphyrins (MTFPP), allow for a disentanglement of the different roles of the hangman motif and the side groups. In agreement with exptl. studies, Fe and Co are the best MHP metal centers to catalyze these reactions. The addn. of the three-dimensional moiety as hangman scaffold does not break the apparently universal energy relation between *OH and *OOH intermediates. However, the hangman motif is found to stabilize the O intermediate, whereas addn. of C6F5 groups reduces the binding energy of all reaction intermediates. The authors' results indicate that the combination of these two effects allow new design possibilities for macromol. systems with enhanced catalytic OER/ORR activity.

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12. 12

    Mahmood, T.; Kosar, N.; Ayub, K. DFT Study of Acceleration of Electrocyclization in Photochromes under Radical Cationic Conditions: Comparison with Recent Experimental Data. Tetrahedron 2017, 73, 3521– 3528,  DOI: 10.1016/j.tet.2017.05.031

    Google Scholar

    12

    DFT study of acceleration of electrocyclization in photochromes under radical cationic conditions: Comparison with recent experimental data

    Mahmood, Tariq; Kosar, Naveen; Ayub, Khurshid

    Tetrahedron (2017), 73 (25), 3521-3528CODEN: TETRAB; ISSN:0040-4020. (Elsevier Ltd.)

    Radical cation formation is proposed for the rapid cyclization of 1, 2-bis[5-phenyl-2-methylthien-3-yl]cyclopentene and oligothiophene functionalized dimethyldihydropyrenes (DMDHP). D. functional theory calcns. have been performed to rationalize the effect of a radical cation on the activation barrier of different classes of electrocyclic photochromes (DHP, dithienylethene, dihydroazulene and fulgide). For exact comparative anal., the activation barrier of neutral (singlet) analogs at the same level of theory are also calcd. In addn., the concerted nature and aromaticity of transition states were investigated with the help of synchronicity (Sy.) and nuclear independent chem. shift values NICS(0) calcns., resp., for both the radical cation and neutral systems. In case of the radical cation, thermal return of CPD to DHP, the activation barrier is very low (ΔH = 3.13 kcal mol-1, ΔG = 4.01 kcal mol-1) as compared to the neutral analog (ΔH = 20.6 kcal mol-1, ΔG = 20.98 kcal mol-1), which is consistent with exptl. observations. Similarly for dithenylethenes, radical cation formation has a large impact on the activation barrier (ΔH = 19.44 kcal mol-1, ΔG = 22.29 kcal mol-1). However, radical cation formation has almost negligible impact on the activation barrier of VHF-DHA and fulgide isomerization. The significant difference has been obsd. for synchronicity and NICS(0) values of all types of photochromes under radical cation conditions as compared to the neutral system.

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13. 13

    Chiatti, F.; Delle Piane, M.; Ugliengo, P.; Corno, M. Water at Hydroxyapatite Surfaces: The Effect of Coverage and Surface Termination as Investigated by All-Electron B3LYP-D* Simulations. Theor. Chem. Acc. 2016, 135, 54,  DOI: 10.1007/s00214-016-1818-8

    Google Scholar

    There is no corresponding record for this reference.
14. 14

    Civalleri, B.; Maschio, L.; Ugliengo, P.; Zicovich-Wilson, C. M. Role of Dispersive Interactions in the CO Adsorption on MgO(001): Periodic B3LYP Calculations Augmented with an Empirical Dispersion Term. Phys. Chem. Chem. Phys. 2010, 12, 6382,  DOI: 10.1039/c001192d

    Google Scholar

    14

    Role of dispersive interactions in the CO adsorption on MgO(001): periodic B3LYP calculations augmented with an empirical dispersion term

    Civalleri, Bartolomeo; Maschio, Lorenzo; Ugliengo, Piero; Zicovich-Wilson, Claudio M.

    Physical Chemistry Chemical Physics (2010), 12 (24), 6382-6386CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)

    Empirically dispersion cor. B3LYP method (i.e. B3LYP-D) is demonstrated to give excellent results for structure, adsorption energy and vibrational frequency shift for the CO mol. adsorbed on the MgO(001) surface, a system considered a challenge for c.d. functional methods. A periodic approach was adopted to model the interaction using a three-layer slab model. For the B3LYP-D* method an interaction energy of -13.1 kJ mol-1 is computed at low-coverage in very good agreement with exptl. evidence (-12.6 kJ mol-1) as well as a pos. CO vibrational shift of 10 cm-1 to be compared with the exptl. value of 14 cm-1.

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15. 15

    Lousada, C. M.; Johansson, A. J.; Brinck, T.; Jonsson, M. Reactivity of Metal Oxide Clusters with Hydrogen Peroxide and Water – a DFT Study Evaluating the Performance of Different Exchange–Correlation Functionals. Phys. Chem. Chem. Phys. 2013, 15, 5539,  DOI: 10.1039/c3cp44559c

    Google Scholar

    15

    Reactivity of metal oxide clusters with hydrogen peroxide and water - a DFT study evaluating the performance of different exchange-correlation functionals

    Lousada, Claudio M.; Johansson, Adam Johannes; Brinck, Tore; Jonsson, Mats

    Physical Chemistry Chemical Physics (2013), 15 (15), 5539-5552CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)

    We have performed a d. functional theory (DFT) investigation of the interactions of H2O2, H2O and HO radicals with clusters of ZrO2, TiO2 and Y2O3. Different modes of H2O adsorption onto the clusters were studied. In almost all the cases the dissociative adsorption is more exothermic than mol. adsorption. At the surfaces where H2O has undergone dissociative adsorption, the adsorption of H2O2 and the transition state for its decompn. are mediated by hydrogen bonding with the surface HO groups. Using the functionals B3LYP, B3LYP-D and M06 with clusters of 26 and 8 units of ZrO2, the M06 functional performed better than B3LYP in describing the reaction of decompn. of H2O2 and the adsorption of H2O. Addnl., we investigated clusters of the type (ZrO2)2, (TiO2)2 and (Y2O3) and the performance of the functionals B3LYP, B3LYP-D, B3LYP*, M06, M06-L, PBE0, PBE and PWPW91 in describing H2O2, H2O and HO√ adsorption and the energy barrier for decompn. of H2O2. The trends obtained for HO√ adsorption onto the clusters are discussed in terms of the ionization energy of the metal cation present in the oxide. In order to correctly account for the existence of an energy barrier for the decompn. of H2O2, the functional used must include Hartree-Fock exchange. Using minimal cluster models, the best performance in describing the energy barrier for H2O2 decompn. was obtained with the M06 and PBE0 functionals - the av. abs. deviations from expts. are 6 kJ mol-1 and 5 kJ mol-1 resp. With the M06 functional and a larger monoclinic (ZrO2)8 cluster model, the performance is in excellent agreement with exptl. data. For the different oxides, PBE0 was found to be the most effective functional in terms of performance and computational time cost.

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16. 16

    Minkin, V. I.; Starikov, A. G.; Starikova, A. A. Computational Insight into Magnetic Behavior and Properties of the Transition Metal Complexes with Redox-Active Ligands: A DFT Approach. Pure Appl. Chem. 2018, 90, 811– 824,  DOI: 10.1515/pac-2017-0803

    Google Scholar

    16

    Computational insight into magnetic behavior and properties of the transition metal complexes with redox-active ligands: a DFT approach

    Minkin, Vladimir I.; Starikov, Andrey G.; Starikova, Alyona A.

    Pure and Applied Chemistry (2018), 90 (5), 811-824CODEN: PACHAS; ISSN:0033-4545. (Walter de Gruyter, Inc.)

    Various aspects related to the use of DFT method for the study of magnetic, geometry and energetic properties of transition metal complexes with redox-active ligands are considered. Particular attention is given to the correct choice of model compds. and methodol. of the calcns.

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17. 17

    Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. J. Chem. Phys. 2010, 132, 154104,  DOI: 10.1063/1.3382344

    Google Scholar

    17

    A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu

    Grimme, Stefan; Antony, Jens; Ehrlich, Stephan; Krieg, Helge

    Journal of Chemical Physics (2010), 132 (15), 154104/1-154104/19CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    The method of dispersion correction as an add-on to std. Kohn-Sham d. functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coeffs. and cutoff radii that are both computed from first principles. The coeffs. for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination nos. (CN). They are used to interpolate between dispersion coeffs. of atoms in different chem. environments. The method only requires adjustment of two global parameters for each d. functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of at. forces. Three-body nonadditivity terms are considered. The method has been assessed on std. benchmark sets for inter- and intramol. noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean abs. deviations for the S22 benchmark set of noncovalent interactions for 11 std. d. functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C6 coeffs. also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in mols. and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems. (c) 2010 American Institute of Physics.

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18. 18

    Starikov, A. G.; Ivanov, D. G.; Starikova, A. A.; Minkin, V. I. Dispersion Interactions in Oligomerization of Metal Diketonates: A DFT Evaluation. Chem. Pap. 2018, 72, 829– 839,  DOI: 10.1007/s11696-017-0225-5

    Google Scholar

    18

    Dispersion interactions in oligomerization of metal diketonates: a DFT evaluation

    Starikov, Andrey G.; Ivanov, Dmitrii G.; Starikova, Alyona A.; Minkin, Vladimir I.

    Chemical Papers (2018), 72 (4), 829-839CODEN: CHPAEG; ISSN:1336-9075. (Springer International Publishing AG)

    The structures of the oligomers of Co(II), Ni(II), Cu(II) and Zn(II) β-diketonates and their stability with respect to dissocn. into the monomeric components were studied with the use of d. functional theory [DFT B3LYP/6-311++G(d,p)] method taking addnl. into account corrections for dispersion interactions in CAM and D3BJ approxns. The calcd. geometries of the oligomers well match those exptl. detd., but stabilization energies obtained at the B3LYP-CAM and B3LYP-D3BJ approxns. are significantly overestimated.

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19. 19

    Zhao, Y.; Truhlar, D. G. Density Functionals with Broad Applicability in Chemistry. Acc. Chem. Res. 2008, 41, 157– 167,  DOI: 10.1021/ar700111a

    Google Scholar

    19

    Density Functionals with Broad Applicability in Chemistry

    Zhao, Yan; Truhlar, Donald G.

    Accounts of Chemical Research (2008), 41 (2), 157-167CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)

    A review. Although d. functional theory is widely used in the computational chem. community, the most popular d. functional, B3LYP, has some serious shortcomings: (i) it is better for main-group chem. than for transition metals; (ii) it systematically underestimates reaction barrier heights; (iii) it is inaccurate for interactions dominated by medium-range correlation energy, such as van der Waals attraction, arom.-arom. stacking, and alkane isomerization energies. We have developed a variety of databases for testing and designing new d. functionals. We used these data to design new d. functionals, called M06-class (and, earlier, M05-class) functionals, for which we enforced some fundamental exact constraints such as the uniform-electron-gas limit and the absence of self-correlation energy. Our M06-class functionals depend on spin-up and spin-down electron densities (i.e., spin densities), spin d. gradients, spin kinetic energy densities, and, for nonlocal (also called hybrid) functionals, Hartree-Fock exchange. We have developed four new functionals that overcome the above-mentioned difficulties: (a) M06, a hybrid meta functional, is a functional with good accuracy "across-the-board" for transition metals, main group thermochem., medium-range correlation energy, and barrier heights; (b) M06-2X, another hybrid meta functional, is not good for transition metals but has excellent performance for main group chem., predicts accurate valence and Rydberg electronic excitation energies, and is an excellent functional for arom.-arom. stacking interactions; (c) M06-L is not as accurate as M06 for barrier heights but is the most accurate functional for transition metals and is the only local functional (no Hartree-Fock exchange) with better across-the-board av. performance than B3LYP; this is very important because only local functionals are affordable for many demanding applications on very large systems; (d) M06-HF has good performance for valence, Rydberg, and charge transfer excited states with minimal sacrifice of ground-state accuracy. In this Account, we compared the performance of the M06-class functionals and one M05-class functional (M05-2X) to that of some popular functionals for diverse databases and their performance on several difficult cases. The tests include barrier heights, conformational energy, and the trend in bond dissocn. energies of Grubbs' ruthenium catalysts for olefin metathesis. Based on these tests, we recommend (1) the M06-2X, BMK, and M05-2X functionals for main-group thermochem. and kinetics, (2) M06-2X and M06 for systems where main-group thermochem., kinetics, and noncovalent interactions are all important, (3) M06-L and M06 for transition metal thermochem., (4) M06 for problems involving multireference rearrangements or reactions where both org. and transition-metal bonds are formed or broken, (5) M06-2X, M05-2X, M06-HF, M06, and M06-L for the study of noncovalent interactions, (6) M06-HF when the use of full Hartree-Fock exchange is important, for example, to avoid the error of self-interaction at long-range, (7) M06-L when a local functional is required, because a local functional has much lower cost for large systems.

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20. 20

    Lonsdale, R.; Harvey, J. N.; Mulholland, A. J. Inclusion of Dispersion Effects Significantly Improves Accuracy of Calculated Reaction Barriers for Cytochrome P450 Catalyzed Reactions. J. Phys. Chem. Lett. 2010, 1, 3232– 3237,  DOI: 10.1021/jz101279n

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    Inclusion of Dispersion Effects Significantly Improves Accuracy of Calculated Reaction Barriers for Cytochrome P450 Catalyzed Reactions

    Lonsdale, Richard; Harvey, Jeremy N.; Mulholland, Adrian J.

    Journal of Physical Chemistry Letters (2010), 1 (21), 3232-3237CODEN: JPCLCD; ISSN:1948-7185. (American Chemical Society)

    Prediction of cytochrome P 450 reactivity is of great importance to the development of new medicinal compds. D. functional theory (DFT) has proven itself as a useful tool in the characterization of the elusive reactive species, compd. I, and of the mechanisms of substrate oxidn. B3LYP is the most widely used d. functional in the study of P 450s; however, a major drawback of B3LYP is its inaccurate treatment of dispersion, leading to discrepancies between expt. and theory in some systems. Recent work has shown that an added empirical dispersion correction to B3LYP (B3LYP-D) yields more promising results for similar systems. In the present work, two previously studied systems, camphor hydroxylation and alkene oxidn., have been recalcd. using B3LYP-D. Our work shows that inclusion of dispersion has a significant effect on the energies and geometries of transition states and encounter complexes; furthermore, an improved agreement with exptl. data is obsd.

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21. 21

    Stein, T.; Kronik, L.; Baer, R. Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theory. J. Am. Chem. Soc. 2009, 131, 2818– 2820,  DOI: 10.1021/ja8087482

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    21

    Reliable prediction of charge transfer excitations in molecular complexes using time-dependent density functional theory

    Stein, Tamar; Kronik, Leeor; Baer, Roi

    Journal of the American Chemical Society (2009), 131 (8), 2818-2820CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    We show how charge transfer excitations at mol. complexes can be calcd. quant. using time-dependent d. functional theory. Predictive power is obtained from range-sepd. hybrid functionals using nonempirical tuning of the range-splitting parameter. Excellent performance of this approach is obtained for a series of complexes composed of various arom. donors and the tetracyanoethylene acceptor, paving the way to systematic nonempirical quant. studies of charge-transfer excitations in real systems.

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22. 22

    Hirao, H. Which DFT Functional Performs Well in the Calculation of Methylcobalamin? Comparison of the B3LYP and BP86 Functionals and Evaluation of the Impact of Empirical Dispersion Correction. J. Phys. Chem. A 2011, 115, 9308– 9313,  DOI: 10.1021/jp2052807

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    22

    Which DFT Functional Performs Well in the Calculation of Methylcobalamin? Comparison of the B3LYP and BP86 Functionals and Evaluation of the Impact of Empirical Dispersion Correction

    Hirao, Hajime

    Journal of Physical Chemistry A (2011), 115 (33), 9308-9313CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    Controversy remains regarding the suitable d. functionals for the calcn. of vitamin B12 systems that contain cobalt. To identify the optimum functionals, geometry optimization calcns. were performed on a full-size model of methylcobalamin (MeCbl) using the B3LYP, B3LYP-D, BP86, and BP86-D methods in conjunction with the 6-31G* basis set. Single-point energy evaluations were also performed with the 6-311+G(2d,p) basis set. Consistent with previous studies, the BP86-optimized geometry showed fairly good agreement with the exptl. geometry. Various factors that may influence the homolytic bond dissocn. energy (BDE) of the Co-C bond of MeCbl were systematically evaluated with these methods. Our anal. demonstrated that dispersion was the largest correction term that influenced the magnitude of BDE. Previous studies have shown that B3LYP significantly underestimates BDE, whereas BP86 gives BDE values that are fairly close to the exptl. values (36-37 kcal/mol). The same trend in the relative magnitudes of the BDEs was obsd. in the present calcns. However, BP86 underestimated the BDE for a full model of MeCbl. When the amt. of Hartree-Fock exchange in the B3LYP functional was reduced to 15% and the dispersion correction was made (i.e., B3LYP*-D), the calcd. BDE was in good accord with exptl. values. B3P86-D also performed well. A detailed anal. was undertaken to det. which atoms in cobalamin have large dispersion interactions with a Me fragment of MeCbl.

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23. 23

    Minenkov, Y.; Occhipinti, G.; Jensen, V. R. Metal–Phosphine Bond Strengths of the Transition Metals: A Challenge for DFT. J. Phys. Chem. A 2009, 113, 11833– 11844,  DOI: 10.1021/jp902940c

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    23

    Metal-phosphine bond strengths of the transition metals: A challenge for DFT

    Minenkov, Yury; Occhipinti, Giovanni; Jensen, Vidar R.

    Journal of Physical Chemistry A (2009), 113 (43), 11833-11844CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    Previous promising tests of the new M06 family of functionals in predicting ruthenium-metal phosphine bond dissocn. energies have been extended to a series of phosphine complexes of chromium, molybdenum, nickel, and ruthenium for which relevant exptl. data are available. In addn. to the M06 family of functionals, bond dissocn. enthalpies have been calcd. using a selection of d. functionals and hybrid functionals based on the generalized gradient approxn. (GGA), and with or without an empirical term (i.e., DFT-D) accounting for long-range dispersion. For the ruthenium complexes, second-order Moller-Plesset perturbation theory (MP2) has also been applied. Electrostatic and nonelectrostatic solvent effects have been estd. using the polarizable continuum model (PCM), allowing for comparison with exptl. data obtained for dissocn. reactions in org. solvents. Whereas the GGA and hybrid-GGA functionals grossly underestimate the abs. metal-phosphine bond enthalpies, with mean unsigned errors (MUEs) for a set of 10 phosphine dissocn. reactions in the range 13-27 kcal/mol, the recently developed DFT-based methods for inclusion of attractive noncovalent interactions and dispersion (the DFT-D and M06 functionals) dramatically improve upon the situation. The best agreement with expt. is obsd. for BLYP-D (MUE = 2.2 kcal/mol), and with the exception for M06-2X, all these methods provide MUEs well below 5 kcal/mol, which should be sufficient for a broad range of applications. The improvements in predicted relative bond enthalpies are less convincing, however. In several cases the GGA and hybrid-GGA functionals are better at reproducing substitution effects than the DFT-D and M06 methods.

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24. 24

    Grimme, S. Accurate Description of van Der Waals Complexes by Density Functional Theory Including Empirical Corrections. J. Comput. Chem. 2004, 25, 1463– 1473,  DOI: 10.1002/jcc.20078

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    24

    Accurate description of van der Waals complexes by density functional theory including empirical corrections

    Grimme, Stefan

    Journal of Computational Chemistry (2004), 25 (12), 1463-1473CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)

    An empirical method to account for van der Waals interactions in practical calcns. in the framework of the d. functional theory (termed DFT-D) was tested for a wide variety of mol. complexes. As in previous schemes, the dispersive energy was described by damped interat. potentials of the form C6R-6. The use of pure, gradient-cor. d. functionals (BLYP and PBE), together with the resoln.-of-the-identity (RI) approxn. for the Coulomb operator, allows very efficient computations for large systems. In contrast to the previous work, extended AO basis sets of polarized TZV or QZV quality were employed, which reduced the basis set superposition error to a negligible extend. By using a global scaling factor for the at. C6 coeffs., the functional dependence of the results could be strongly reduced. The "double counting" of correlation effects for strongly bound complexes was found to be insignificant if steep damping functions were employed. The method was applied to a total of 29 complexes of atoms and small mols. (Ne, CH4, NH3, H2O, CH3F, N2, F2, formic acid, ethene, and ethine) with each other and with benzene, to benzene, naphthalene, pyrene, and coronene dimers, the naphthalene trimer, coronene·H2O and four H-bonded and stacked DNA base pairs (AT and GC). In almost all cases, very good agreement with reliable theor. or exptl. results for binding energies and intermol. distances is obtained. For stacked arom. systems and the important base pairs, the DFT-D-BLYP model seems to be even superior to std. MP2 treatments that systematically over-bind. The good results obtained suggest the approach as a practical tool to describe the properties of many important van der Waals systems in chem. Furthermore, the DFT-D data may either be used to calibrate much simpler (e.g., force-field) potentials or the optimized structures can be used as input for more accurate ab initio calcns. of the interaction energies.

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25. 25

    Grimme, S. Semiempirical GGA-Type Density Functional Constructed with a Long-Range Dispersion Correction. J. Comput. Chem. 2006, 27, 1787– 1799,  DOI: 10.1002/jcc.20495

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    25

    Semiempirical GGA-type density functional constructed with a long-range dispersion correction

    Grimme, Stefan

    Journal of Computational Chemistry (2006), 27 (15), 1787-1799CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)

    A new d. functional (DF) of the generalized gradient approxn. (GGA) type for general chem. applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C6·R-6. A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common d. functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on std. thermochem. benchmark sets, for 40 noncovalently bound complexes, including large stacked arom. mols. and group II element clusters, and for the computation of mol. geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for std. functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean abs. deviation of only 3.8 kcal mol-1. The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the av. CCSD(T) accuracy. The basic strategy in the development to restrict the d. functional description to shorter electron correlation lengths scales and to describe situations with medium to large interat. distances by damped C6·R-6 terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chem. method for large systems where dispersion forces are of general importance.

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26. 26

    Johnson, E. R.; Becke, A. D. A Post-Hartree-Fock Model of Intermolecular Interactions: Inclusion of Higher-Order Corrections. J. Chem. Phys. 2006, 124, 174104,  DOI: 10.1063/1.2190220

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    26

    A post-Hartree-Fock model of intermolecular interactions: Inclusion of higher-order corrections

    Johnson, Erin R.; Becke, Axel D.

    Journal of Chemical Physics (2006), 124 (17), 174104/1-174104/9CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    We have previously demonstrated that the dipole moment of the exchange hole can be used to derive intermol. C6 dispersion coeffs. [J. Chem. Phys. 122, 154104 (2005)]. This was subsequently the basis for a novel post-Hartree-Fock model of intermol. interactions [J. Chem. Phys. 123, 024101 (2005)]. In the present work, the model is extended to include higher-order dispersion coeffs. C8 and C10. The extended model performs very well for prediction of intermonomer sepns. and binding energies of 45 van der Waals complexes. In particular, it performs twice as well as basis-set extrapolated MP2 theory for dispersion-bound complexes, with minimal computational cost.

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27. 27

    Fey, N.; Ridgway, B. M.; Jover, J.; McMullin, C. L.; Harvey, J. N. Organometallic Reactivity: The Role of Metal–Ligand Bond Energies from a Computational Perspective. Dalton Trans. 2011, 40, 11184,  DOI: 10.1039/c1dt10909j

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    27

    Organometallic reactivity: the role of metal-ligand bond energies from a computational perspective

    Fey, Natalie; Ridgway, Benjamin M.; Jover, Jesus; McMullin, Claire L.; Harvey, Jeremy N.

    Dalton Transactions (2011), 40 (42), 11184-11191CODEN: DTARAF; ISSN:1477-9226. (Royal Society of Chemistry)

    A review; the assocn. and dissocn. of ligands plays a vital role in detg. the reactivity of organometallic catalysts. Computational studies with d. functional theory often fail to reproduce exptl. metal-ligand bond energies, but recently functionals which better capture dispersion effects have been developed. Here we explore their application and discuss future challenges for computational studies of organometallic catalysis.

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28. 28

    Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N., Staroverov, V. N., Normand, R. K. J., Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Rega, M. C. N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Gomperts, J. J. R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J. D. J. F. Gaussian 09, Revision D.01; Gaussian, Inc.: Wallingford CT, 2009.

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29. 29

    Mo, Y.; Tian, G.; Car, R.; Staroverov, V. N.; Scuseria, G. E.; Tao, J. Performance of a Nonempirical Density Functional on Molecules and Hydrogen-Bonded Complexes. J. Chem. Phys. 2016, 145, 234306,  DOI: 10.1063/1.4971853

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    29

    Performance of a nonempirical density functional on molecules and hydrogen-bonded complexes

    Mo, Yuxiang; Tian, Guocai; Car, Roberto; Staroverov, Viktor N.; Scuseria, Gustavo E.; Tao, Jianmin

    Journal of Chemical Physics (2016), 145 (23), 234306/1-234306/9CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    Recently, Tao and Mo derived a meta-generalized gradient approxn. functional based on a model exchange-correlation hole. In this work, the performance of this functional is assessed on std. test sets, using the 6-311++G(3df,3pd) basis set. These test sets include 223 G3/99 enthalpies of formation, 99 atomization energies, 76 barrier heights, 58 electron affinities, 8 proton affinities, 96 bond lengths, 82 harmonic vibrational frequencies, 10 hydrogen-bonded mol. complexes, and 22 at. excitation energies. Our calcns. show that the Tao-Mo functional can achieve high accuracy for most properties considered, relative to the local spin-d. approxn., Perdew-Burke-Ernzerhof, and Tao-Perdew-Staroverov-Scuseria functionals. In particular, it yields the best accuracy for proton affinities, harmonic vibrational frequencies, hydrogen-bond dissocn. energies and bond lengths, and at. excitation energies. (c) 2016 American Institute of Physics.

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30. 30

    Zhao, Y.; Truhlar, D. G. A New Local Density Functional for Main-Group Thermochemistry, Transition Metal Bonding, Thermochemical Kinetics, and Noncovalent Interactions. J. Chem. Phys. 2006, 125, 194101,  DOI: 10.1063/1.2370993

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    30

    A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions

    Zhao, Yan; Truhlar, Donald G.

    Journal of Chemical Physics (2006), 125 (19), 194101/1-194101/18CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    We present a new local d. functional, called M06-L, for main-group and transition element thermochem., thermochem. kinetics, and noncovalent interactions. The functional is designed to capture the main dependence of the exchange-correlation energy on local spin d., spin d. gradient, and spin kinetic energy d., and it is parametrized to satisfy the uniform-electron-gas limit and to have good performance for both main-group chem. and transition metal chem. The M06-L functional and 14 other functionals have been comparatively assessed against 22 energetic databases. Among the tested functionals, which include the popular B3LYP, BLYP, and BP86 functionals as well as our previous M05 functional, the M06-L functional gives the best overall performance for a combination of main-group thermochem., thermochem. kinetics, and organometallic, inorganometallic, biol., and noncovalent interactions. It also does very well for predicting geometries and vibrational frequencies. Because of the computational advantages of local functionals, the present functional should be very useful for many applications in chem., esp. for simulations on moderate-sized and large systems and when long time scales must be addressed.

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31. 31

    Tao, J.; Perdew, J. P.; Staroverov, V. N.; Scuseria, G. E. Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids. Phys. Rev. Lett. 2003, 91, 146401,  DOI: 10.1103/PhysRevLett.91.146401

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    31

    Climbing the Density Functional Ladder: Nonempirical Meta-Generalized Gradient Approximation Designed for Molecules and Solids

    Tao, Jianmin; Perdew, John P.; Staroverov, Viktor N.; Scuseria, Gustavo E.

    Physical Review Letters (2003), 91 (14), 146401/1-146401/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)

    The electron d., its gradient, and the Kohn-Sham orbital kinetic energy d. are the local ingredients of a meta-generalized gradient approxn. (meta-GGA). We construct a meta-GGA d. functional for the exchange-correlation energy that satisfies exact constraints without empirical parameters. The exchange and correlation terms respect two paradigms: one- or two-electron densities and slowly varying densities, and so describe both mols. and solids with high accuracy, as shown by extensive numerical tests. This functional completes the third rung of "Jacob's ladder" of approxns., above the local spin d. and GGA rungs.

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32. 32

    Zhao, Y.; Lynch, B. J.; Truhlar, D. G. Development and Assessment of a New Hybrid Density Functional Model for Thermochemical Kinetics. J. Phys. Chem. A 2004, 108, 2715– 2719,  DOI: 10.1021/jp049908s

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    32

    Development and Assessment of a New Hybrid Density Functional Model for Thermochemical Kinetics

    Zhao, Yan; Lynch, Benjamin J.; Truhlar, Donald G.

    Journal of Physical Chemistry A (2004), 108 (14), 2715-2719CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    A new hybrid Hartree-Fock-d. functional model called the Becke88-Becke95 1-parameter model for kinetics (BB1K) was optimized against a database of three forward barrier heights, three reverse barrier heights, and three energies of reaction for the reactions in the BH6 representative barrier height database. We then assessed the newly developed BB1K method against a saddle point geometries database, a database of 42 barrier heights, the AE6 representative atomization energy database, a mol. geometries data set, and a set of 13 zero point energies. The results show that BB1K can give excellent saddle point geometries and barrier heights, and its performance for calcg. atomization energies is 40% better than MPW1K. Using a mean mean unsigned error criterion that equally wts. the errors in barrier heights and in bond energies, the new BB1K method outperforms all other DFT and hybrid DFT methods by a large margin, and we therefore conclude that it is the best d. functional-type method for thermochem. kinetics.

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33. 33

    Becke, A. D. New Mixing of Hartree–Fock and Local Density-functional Theories. J. Chem. Phys. 1993, 98, 1372– 1377,  DOI: 10.1063/1.464304

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    33

    A new mixing of Hartree-Fock and local-density-functional theories

    Becke, Axel D.

    Journal of Chemical Physics (1993), 98 (2), 1372-7CODEN: JCPSA6; ISSN:0021-9606.

    Previous attempts to combine the Hartree-Fock theory with the local d.-functional theory were unsuccessful in applications to mol. bonding. A new coupling is presented of these two theories that maintains their simplicity and computational efficiency, and yet greatly improves their predictive power. Very encouraging results of tests on atomization energies, ionization potentials, and proton affinities are reported, and the potential for future development is discussed.

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34. 34

    Schmider, H. L.; Becke, A. D. Optimized Density Functionals from the Extended G2 Test Set. J. Chem. Phys. 1998, 108, 9624– 9631,  DOI: 10.1063/1.476438

    Google Scholar

    34

    Optimized density functionals from the extended G2 test set

    Schmider, Hartmut L.; Becke, Axel D.

    Journal of Chemical Physics (1998), 108 (23), 9624-9631CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    A recently suggested procedure for the systematic optimization of gradient-cor. exchange-correlation functionals [A. D. Becke, J. Chem. Phys. 107, 8554 (1997)] has been applied to the extended G2 test set [L. A. Curtiss et al., J. Chem. Phys. 106, 1063 (1997)], which consists of the std. heats of formation of 148 mols. The limit of reprodn. of the exptl. data in this test set is found to be 1.78 kcal/mol mean abs. error, with a max. of 8.89 kcal/mol error for the ozone mol. This compares rather well with previous results for G2 theory itself (1.58 and 8.2 kcal/mol, resp.). We show that fair stability can be obtained by our optimization procedure.

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35. 35

    Wilson, P. J.; Bradley, T. J.; Tozer, D. J. Hybrid Exchange-Correlation Functional Determined from Thermochemical Data and Ab Initio Potentials. J. Chem. Phys. 2001, 115, 9233– 9242,  DOI: 10.1063/1.1412605

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    35

    Hybrid exchange-correlation functional determined from thermochemical data and ab initio potentials

    Wilson, Philip J.; Bradley, Thomas J.; Tozer, David J.

    Journal of Chemical Physics (2001), 115 (20), 9233-9242CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    Multiplicative potentials, appropriate for adding to the non-multiplicative fractional orbital exchange term in the Kohn-Sham equations, are detd. from correlated ab initio electron densities. The potentials are examd. graphically and are used in conjunction with conventional thermochem. data to det. a new hybrid exchange-correlation functional, denoted B97-2. Calcns. using B97-2 are compared with those from (a) the B97-1 functional [J. Chem. Phys. 109, 6264 (1998)], which has the same functional form and fraction of orbital exchange, but was fitted to just thermochem. data; and (b) the widely used B3LYP functional [J. Chem. Phys. 98, 5648 (1993)]. B97-2 atomization energies are close to those from B97-1; total electronic energies and ionization potentials are less accurate, but remain an improvement over B3LYP. Mol. structures from all three functionals are comparable. Static isotropic polarizabilities improve from B3LYP to B97-1 to B97-2; the B97-2 functional underestimates exptl. values, which is consistent with the neglect of zero-point vibrational corrections. NMR shielding consts. - detd. as the conventional second deriv. of the electronic energy - improve from B3LYP to B97-1 to B97-2. Shieldings detd. directly from these DFT electron densities using the recently proposed MKS approach [Chem. Phys. Lett. 337, 341 (2001)] are two to three times more accurate than the conventional shieldings, and exhibit an analogous improvement across the three functionals. Classical reaction barriers for sixteen chem. reactions improve significantly from B3LYP to B97-1 to B97-2. The introduction of multiplicative potentials into semi-empirical hybrid functional development therefore appears beneficial.

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36. 36

    Adamo, C.; Barone, V. Toward Reliable Density Functional Methods without Adjustable Parameters: The PBE0 Model. J. Chem. Phys. 1999, 110, 6158– 6170,  DOI: 10.1063/1.478522

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    36

    Toward reliable density functional methods without adjustable parameters: the PBE0 model

    Adamo, Carlo; Barone, Vincenzo

    Journal of Chemical Physics (1999), 110 (13), 6158-6170CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    We present an anal. of the performances of a parameter free d. functional model (PBE0) obtained combining the so called PBE generalized gradient functional with a predefined amt. of exact exchange. The results obtained for structural, thermodn., kinetic and spectroscopic (magnetic, IR and electronic) properties are satisfactory and not far from those delivered by the most reliable functionals including heavy parameterization. The way in which the functional is derived and the lack of empirical parameters fitted to specific properties make the PBE0 model a widely applicable method for both quantum chem. and condensed matter physics.

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37. 37

    Zhao, Y.; Schultz, N. E.; Truhlar, D. G. Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions. J. Chem. Theory Comput. 2006, 2, 364– 382,  DOI: 10.1021/ct0502763

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    37

    Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions

    Zhao, Yan; Schultz, Nathan E.; Truhlar, Donald G.

    Journal of Chemical Theory and Computation (2006), 2 (2), 364-382CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)

    We present a new hybrid meta exchange-correlation functional, called M05-2X, for thermochem., thermochem. kinetics, and noncovalent interactions. We also provide a full discussion of the new M05 functional, previously presented in a short communication. The M05 functional was parametrized including both metals and nonmetals, whereas M05-2X is a high-nonlocality functional with double the amt. of nonlocal exchange (2X) that is parametrized only for nonmetals. In particular, M05 was parametrized against 35 data values, and M05-2X is parametrized against 34 data values. Both functionals, along with 28 other functionals, have been comparatively assessed against 234 data values: the MGAE109/3 main-group atomization energy database, the IP13/3 ionization potential database, the EA13/3 electron affinity database, the HTBH38/4 database of barrier height for hydrogen-transfer reactions, five noncovalent databases, two databases involving metal-metal and metal-ligand bond energies, a dipole moment database, a database of four alkyl bond dissocn. energies of alkanes and ethers, and three total energies of one-electron systems. We also tested the new functionals and 12 others for eight hydrogen-bonding and stacking interaction energies in nucleobase pairs, and we tested M05 and M05-2X and 19 other functionals for the geometry, dipole moment, and binding energy of HCN-BF3, which has recently been shown to be a very difficult case for d. functional theory. We tested eight functionals for four more alkyl bond dissocn. energies, and we tested 12 functionals for several addnl. bond energies with varying amts. of multireference character. On the basis of all the results for 256 data values in 18 databases in the present study, we recommend M05-2X, M05, PW6B95, PWB6K, and MPWB1K for general-purpose applications in thermochem., kinetics, and noncovalent interactions involving nonmetals and we recommend M05 for studies involving both metallic and nonmetallic elements. The M05 functional, essentially uniquely among the functionals with broad applicability to chem., also performs well not only for main-group thermochem. and radical reaction barrier heights but also for transition-metal-transition-metal interactions. The M05-2X functional has the best performance for thermochem. kinetics, noncovalent interactions (esp. weak interaction, hydrogen bonding, π···π stacking, and interactions energies of nucleobases), and alkyl bond dissocn. energies and the best composite results for energetics, excluding metals.

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38. 38

    Zhao, Y.; Truhlar, D. G. The M06 Suite of Density Functionals for Main Group Thermochemistry, Thermochemical Kinetics, Noncovalent Interactions, Excited States, and Transition Elements: Two New Functionals and Systematic Testing of Four M06-Class Functionals and 12 Other Function. Theor. Chem. Acc. 2008, 120, 215– 241,  DOI: 10.1007/s00214-007-0310-x

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    38

    The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals

    Zhao, Yan; Truhlar, Donald G.

    Theoretical Chemistry Accounts (2008), 120 (1-3), 215-241CODEN: TCACFW; ISSN:1432-881X. (Springer GmbH)

    We present two new hybrid meta exchange-correlation functionals, called M06 and M06-2X. The M06 functional is parametrized including both transition metals and nonmetals, whereas the M06-2X functional is a high-nonlocality functional with double the amt. of nonlocal exchange (2X), and it is parametrized only for nonmetals. The functionals, along with the previously published M06-L local functional and the M06-HF full-Hartree-Fock functionals, constitute the M06 suite of complementary functionals. We assess these four functionals by comparing their performance to that of 12 other functionals and Hartree-Fock theory for 403 energetic data in 29 diverse databases, including ten databases for thermochem., four databases for kinetics, eight databases for noncovalent interactions, three databases for transition metal bonding, one database for metal atom excitation energies, and three databases for mol. excitation energies. We also illustrate the performance of these 17 methods for three databases contg. 40 bond lengths and for databases contg. 38 vibrational frequencies and 15 vibrational zero point energies. We recommend the M06-2X functional for applications involving main-group thermochem., kinetics, noncovalent interactions, and electronic excitation energies to valence and Rydberg states. We recommend the M06 functional for application in organometallic and inorganometallic chem. and for noncovalent interactions.

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39. 39

    Zhao, Y.; Truhlar, D. G. Comparative DFT Study of van Der Waals Complexes: Rare-Gas Dimers, Alkaline-Earth Dimers, Zinc Dimer, and Zinc-Rare-Gas Dimers. J. Phys. Chem. A 2006, 110, 5121– 5129,  DOI: 10.1021/jp060231d

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    39

    Comparative DFT Study of van der Waals Complexes: Rare-Gas Dimers, Alkaline-Earth Dimers, Zinc Dimer, and Zinc-Rare-Gas Dimers

    Zhao, Yan; Truhlar, Donald G.

    Journal of Physical Chemistry A (2006), 110 (15), 5121-5129CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    Recent interest in the application of d. functional theory prompted us to test various functionals for the van der Waals interactions in the rare-gas dimers, the alk.-earth metal dimers, zinc dimer, and zinc-rare-gas dimers. In the present study, we report such tests for 18 DFT functionals, including both some very recent functionals and some well-established older ones. We draw the following conclusions based on the mean errors in binding energies and complex geometries: (1) B97-1 gives the best performance for predicting the geometry of rare-gas dimers, whereas M05-2X and B97-1 give the best energetics for rare-gas dimers; (2) PWB6K gives the best performance for the prediction of the geometry of the alk.-earth metal dimers, zinc dimers, and zinc-rare-gas dimers. M05-2X gives the best energetics for the metal dimers, whereas B97-1 gives the best energetics for the zinc-rare-gas dimers; (3) The M05 functional is unique in providing good accuracy for both covalent transition-metal dimers and van der Waals metal dimers; (4) The combined mean percentage unsigned error in geometries and energetics shows that M05-2X and MPWB1K are the overall best methods for the prediction of van der Waals interactions in metal and rare-gas van der Waals dimers.

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40. 40

    Grimme, S.; Ehrlich, S.; Goerigk, L. Effect of the Damping Function in Dispersion Corrected Density Functional Theory. J. Comput. Chem. 2011, 32, 1456– 1465,  DOI: 10.1002/jcc.21759

    Google Scholar

    40

    Effect of the damping function in dispersion corrected density functional theory

    Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars

    Journal of Computational Chemistry (2011), 32 (7), 1456-1465CODEN: JCCHDD; ISSN:0192-8651. (John Wiley & Sons, Inc.)

    It is shown by an extensive benchmark on mol. energy data that the math. form of the damping function in DFT-D methods has only a minor impact on the quality of the results. For 12 different functionals, a std. "zero-damping" formula and rational damping to finite values for small interat. distances according to Becke and Johnson (BJ-damping) has been tested. The same (DFT-D3) scheme for the computation of the dispersion coeffs. is used. The BJ-damping requires one fit parameter more for each functional (three instead of two) but has the advantage of avoiding repulsive interat. forces at shorter distances. With BJ-damping better results for nonbonded distances and more clear effects of intramol. dispersion in four representative mol. structures are found. For the noncovalently-bonded structures in the S22 set, both schemes lead to very similar intermol. distances. For noncovalent interaction energies BJ-damping performs slightly better but both variants can be recommended in general. The exception to this is Hartree-Fock that can be recommended only in the BJ-variant and which is then close to the accuracy of cor. GGAs for non-covalent interactions. According to the thermodn. benchmarks BJ-damping is more accurate esp. for medium-range electron correlation problems and only small and practically insignificant double-counting effects are obsd. It seems to provide a phys. correct short-range behavior of correlation/dispersion even with unmodified std. functionals. In any case, the differences between the two methods are much smaller than the overall dispersion effect and often also smaller than the influence of the underlying d. functional. © 2011 Wiley Periodicals, Inc.; J. Comput. Chem., 2011.

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41. 41

    Chai, J.-D.; Head-Gordon, M. Long-Range Corrected Hybrid Density Functionals with Damped Atom–Atom Dispersion Corrections. Phys. Chem. Chem. Phys. 2008, 10, 6615,  DOI: 10.1039/b810189b

    Google Scholar

    41

    Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections

    Chai, Jeng-Da; Head-Gordon, Martin

    Physical Chemistry Chemical Physics (2008), 10 (44), 6615-6620CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)

    We report re-optimization of a recently proposed long-range cor. (LC) hybrid d. functional [J.-D. Chai and M. Head-Gordon, J. Chem. Phys., 2008, 128, 084106] to include empirical atom-atom dispersion corrections. The resulting functional, ωB97X-D yields satisfactory accuracy for thermochem., kinetics, and non-covalent interactions. Tests show that for non-covalent systems, ωB97X-D shows slight improvement over other empirical dispersion-cor. d. functionals, while for covalent systems and kinetics it performs noticeably better. Relative to our previous functionals, such as ωB97X, the new functional is significantly superior for non-bonded interactions, and very similar in performance for bonded interactions.

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42. 42

    Ditchfield, R.; Hehre, W. J.; Pople, J. A. Self-Consistent Molecular-Orbital Methods. IX. An Extended Gaussian-Type Basis for Molecular-Orbital Studies of Organic Molecules. J. Chem. Phys. 1971, 54, 724– 728,  DOI: 10.1063/1.1674902

    Google Scholar

    42

    Self-consistent molecular-orbital methods. IX. Extended Gaussian-type basis for molecular-orbital studies of organic molecules

    Ditchfield, R.; Hehre, Warren J.; Pople, John A.

    Journal of Chemical Physics (1971), 54 (2), 724-8CODEN: JCPSA6; ISSN:0021-9606.

    An extended basis set of at. functions expressed as fixed linear combinations of Gaussian functions is presented for H and the first-row atoms C to F. In this set. described as 4-31 G, each inner shell is represented by a single basis function taken as a sum of 4 Gaussians, and each valence orbital is split into inner and outer parts described by 3 and 1 Gaussian function, resp. The expansion coeffs. and Gaussian exponents are detd. by minimizing the total calcd. energy of the at. ground state. This basis set is then used in single-determinant MO studies of a group of small polyat. mols. Optimization of valence-shell scaling factors shows that considerable rescaling of at. functions occurs in mols., the largest effects being obsd. for H and C. However, the range of optimum scale factors for each atom is small enough to allow the selection of a std. mol. set. The use of this std. basis gives theoretical equil. geometries in reasonable agreement with expt.

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43. 43

    Hay, P. J.; Wadt, W. R. Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for the Transition Metal Atoms Sc to Hg. J. Chem. Phys. 1985, 82, 270– 283,  DOI: 10.1063/1.448799

    Google Scholar

    43

    Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms scandium to mercury

    Hay, P. Jeffrey; Wadt, Willard R.

    Journal of Chemical Physics (1985), 82 (1), 270-83CODEN: JCPSA6; ISSN:0021-9606.

    Ab initio effective core potentials (ECP's) were generated to replace the Coulomb, exchange, and core-orthogonality effects of the chem. inert core electron in the transition metal atoms Sc to Hg. For the second and third transition series relative ECP's were generated which also incorporate the mass-velocity and Darwin relativistic effects into the potential. The ab initio ECP's should facilitate valence electron calcns. on mols. contg. transition-metal atoms with accuracies approaching all-electron calcns. at a fraction of the computational cost. Analytic fits to the potentials are presented for use in multicenter integral evaluation. Gaussian orbital valence basis sets are developed for the (3d,4s,4p), (4d,5s,5p), and (5d,6s,6p) orbitals of the first, second, and third transition series atoms, resp. All-electron and valence-electron at. excitation energies are also compared for the low-lying states of Sc-Hg, and the valence-electron calcns. reproduce the all-electron excitation energies (typically within a few tenths of an eV).

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44. 44

    Andrae, D.; Häuβermann, U.; Dolg, M.; Stoll, H.; Preuβ, H. Energy-Adjustedab Initio Pseudopotentials for the Second and Third Row Transition Elements. Theor. Chim. Acta 1990, 77, 123– 141,  DOI: 10.1007/BF01114537

    Google Scholar

    44

    Energy-adjusted ab initio pseudopotentials for the second and third row transition elements

    Andrae, D.; Haeussermann, U.; Dolg, M.; Stoll, H.; Preuss, H.

    Theoretica Chimica Acta (1990), 77 (2), 123-41CODEN: TCHAAM; ISSN:0040-5744.

    Nonrelativistic and quasirelativistic ab initio pseudopotentials substituting the M(z-28)+-core orbitals of the second row transition elements and M(z-60)+-core orbitals of the third row transition elements, resp., and optimized (8s7p6d)/[6s5p3d]-GTO valence basis sets for use in mol. calcns. have been generated. Addnl., corresponding spin-orbit operators have also been derived. At. excitation and ionization energies from numerical HF as well as from SCF pseudopotential calcns. using the derived basis sets differ in most cases by less than 0.1 eV from corresponding numerical all-electron results. Spin-orbit splittings for low-lying states are in reasonable agreement with corresponding all-electron Dirac-Fock (DF) results.

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45. 45

    Schwerdtfeger, P. The Pseudopotential Approximation in Electronic Structure Theory. ChemPhysChem 2011, 12, 3143– 3155,  DOI: 10.1002/cphc.201100387

    Google Scholar

    45

    The Pseudopotential Approximation in Electronic Structure Theory

    Schwerdtfeger, Peter

    ChemPhysChem (2011), 12 (17), 3143-3155CODEN: CPCHFT; ISSN:1439-4235. (Wiley-VCH Verlag GmbH & Co. KGaA)

    A review. A short review is presented on one of the most successful theories for electronic structure calcns., the pseudopotential approxn., originally introduced by Hans G. A. Hellmann in 1934. Recent developments in relativistic quantum theory allow for the accurate adjustment of pseudopotential parameters to valence spectra, producing results for properties of atoms, mols., and the solid-state in excellent agreement with more accurate all-electron results if a small-core definition is used. Thus the relativistic pseudopotential approxn. is now the most widely applied method for systems contg. heavy elements.

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46. 46

    Lynch, B. J.; Zhao, Y.; Truhlar, D. G. Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory. J. Phys. Chem. A 2003, 107, 1384– 1388,  DOI: 10.1021/jp021590l

    Google Scholar

    46

    Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory

    Lynch, Benjamin J.; Zhao, Yan; Truhlar, Donald G.

    Journal of Physical Chemistry A (2003), 107 (9), 1384-1388CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    The addn. of diffuse functions to a double-ζ basis set is more important than increasing to a triple-ζ basis when calcg. reaction energies, reaction barrier heights, and conformational energies with d. functional theory, in particular with the modified Perdew-Wang d. functional. Diffuse basis functions are vital to describe the relative energies between reactants, products, and transition states in isogyric reactions, and they provide enormous improvement in accuracy for conformational equil., using 1, 2-ethanediol and butadiene as examples. As a byproduct of the present study, the authors present a 1-parameter hybrid d. functional method optimized for sugars and sugar-like mols.; this is called MPW1S.

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47. 47

    Lanci, M. P.; Roth, J. P. Oxygen Isotope Effects upon Reversible O 2 -Binding Reactions: Characterizing Mononuclear Superoxide and Peroxide Structures. J. Am. Chem. Soc. 2006, 128, 16006– 16007,  DOI: 10.1021/ja0669326

    Google Scholar

    47

    Oxygen Isotope Effects upon Reversible O2-Binding Reactions: Characterizing Mononuclear Superoxide and Peroxide Structures

    Lanci, Michael P.; Roth, Justine P.

    Journal of the American Chemical Society (2006), 128 (50), 16006-16007CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    Identifying intermediates in catalytic oxidn. reactions requires the development of new probes of structure and mechanism. Reported here are proof-of-concept studies of oxygen (18O) isotope effects upon reversible O2-binding reactions of classic inorg. compds. It is shown that the 18O equil. isotope effects may be used to differentiate structures where O2 is bound as a side-on peroxide ligand vs. an end-on superoxide ligand. The application of 18O equil. isotope effects to the interpretation of 18O kinetic isotope effects and the study of O2 activation mechanisms is also discussed.

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48. 48

    Vaska, L.; Chen, L. S.; Senoff, C. V. Oxygen-Carrying Iridium Complexes: Kinetics, Mechanism, and Thermodynamics. Science 1971, 174, 587– 589,  DOI: 10.1126/science.174.4009.587

    Google Scholar

    48

    Oxygen-carrying iridium complexes. Kinetics, mechanism, and thermodynamics

    Vaska, L.; Chen, Loomis S.; Senoff, C. V.

    Science (Washington, DC, United States) (1971), 174 (4009), 587-9CODEN: SCIEAS; ISSN:0036-8075.

    The rates of oxygenation and deoxygenation of a series of Ir complexes increase and decrease, resp., with increasing electron-releasing tendency of the anionic ligands (A) attached to the metal atom in the O-carrying compds. [IrA(CO)(Ph3P)2]. Calcd. heats of oxygenation (-ΔH02), related to Ir-O2 bond energies, are proportional to the previously reported O-O bond lengths in the O adducts, [O2IrA(CO)(Ph3P)2].

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49. 49

    Saracini, C.; Liakos, D. G.; Zapata Rivera, J. E.; Neese, F.; Meyer, G. J.; Karlin, K. D. Excitation Wavelength Dependent O 2 Release from Copper(II)–Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies. J. Am. Chem. Soc. 2014, 136, 1260– 1263,  DOI: 10.1021/ja4115314

    Google Scholar

    49

    Excitation Wavelength Dependent O2 Release from Copper(II)-Superoxide Compounds: Laser Flash-Photolysis Experiments and Theoretical Studies

    Saracini, Claudio; Liakos, Dimitrios G.; Zapata Rivera, Jhon E.; Neese, Frank; Meyer, Gerald J.; Karlin, Kenneth D.

    Journal of the American Chemical Society (2014), 136 (4), 1260-1263CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    Irradn. of the Cu(II)-superoxide synthetic complexes [(TMG3tren)-CuII(O2)]+ (1) and [(PV-TMPA)-CuII(O2)]+ (2) with visible light resulted in direct photogeneration of O2 gas at low temp. (from -40 to -70° C for 1 and from -125 to -135° C for 2) in 2-methyltetrahydrofuran (MeTHF) solvent (TMG3tren = 1,1,1-tris-{2-[N2-1,1,3,3-tetramethylguanidino]-ethyl}-amine; PV-TMPA = bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]methyl}amine) . The yield of O2 release was wavelength dependent: λexc = 436 nm, .vphi. = 0.29 (for 1), .vphi. = 0.11 (for 2), and λexc = 683 nm, .vphi. = 0.035 (for 1), .vphi. = 0.078 (for 2), which was followed by fast O2-recombination with [(TMG3tren)-CuI]+ (3) and [(PV-TMPA)-CuI]+ (4). Enthalpic barriers for O2 rebinding to the copper-(I) center (∼10 kJ mol-1) and for O2 dissocn. from the superoxide compd. 1 (45 kJ mol-1) were detd. TD-DFT studies, carried out for 1, support the exptl. results confirming the dissociative character of the excited states formed upon blue- or red-light laser excitation.

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50. 50

    Mardirossian, N.; Head-Gordon, M. Thirty Years of Density Functional Theory in Computational Chemistry: An Overview and Extensive Assessment of 200 Density Functionals. Mol. Phys. 2017, 115, 2315– 2372,  DOI: 10.1080/00268976.2017.1333644

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    Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals

    Mardirossian, Narbe; Head-Gordon, Martin

    Molecular Physics (2017), 115 (19), 2315-2372CODEN: MOPHAM; ISSN:0026-8976. (Taylor & Francis Ltd.)

    In the past 30 years, Kohn-Sham d. functional theory has emerged as the most popular electronic structure method in computational chem. To assess the ever-increasing no. of approx. exchange-correlation functionals, this review benchmarks a total of 200 d. functionals on a mol. database (MGCDB84) of nearly 5000 data points. The database employed, provided as Supplemental Data, is comprised of 84 data-sets and contains non-covalent interactions, isomerisation energies, thermochem., and barrier heights. In addn., the evolution of non-empirical and semi-empirical d. functional design is reviewed, and guidelines are provided for the proper and effective use of d. functionals. The most promising functional considered is ωB97M-V, a range-sepd. hybrid meta-GGA with VV10 nonlocal correlation, designed using a combinatorial approach. From the local GGAs, B97-D3, revPBE-D3, and BLYP-D3 are recommended, while from the local meta-GGAs, B97M-rV is the leading choice, followed by MS1-D3 and M06-L-D3. The best hybrid GGAs are ωB97X-V, ωB97X-D3, and ωB97X-D, while useful hybrid meta-GGAs (besides ωB97M-V) include ωM05-D, M06-2X-D3, and MN15. Ultimately, today's state-of-the-art functionals are close to achieving the level of accuracy desired for a broad range of chem. applications, and the principal remaining limitations are assocd. with systems that exhibit significant self-interaction/delocalisation errors and/or strong correlation effects.

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    Kosar, N.; Ayub, K.; Mahmood, T. Accurate Theoretical Method for Homolytic Cleavage of C Sn Bond: A Benchmark Approach. Comput. Theor. Chem. 2018, 1140, 134– 144,  DOI: 10.1016/j.comptc.2018.08.003

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    51

    Accurate theoretical method for homolytic cleavage of C-Sn bond: A benchmark approach

    Kosar, Naveen; Ayub, Khurshid; Mahmood, Tariq

    Computational & Theoretical Chemistry (2018), 1140 (), 134-144CODEN: CTCOA5; ISSN:2210-271X. (Elsevier B.V.)

    Stille coupling is a well-known cross coupling reaction, where the rate detn. step is the dissocn. of carbon stannous (C-Sn) bond. The organotin compds. are also used as precursors in the manufg. of tin oxide films, solar cells, gas sensors, flat panel display technol. and low emission glass materials, etc. The reactivity of organotin compds. has direct relationship with the homolytic cleavage of C-Sn bond. Therefore, accurate detn. of C-Sn bond has direct relevance in understanding many phenomena. The current benchmark study is aimed at finding out the accurate theor. method for the homolytic cleavage (bond dissocn. energy) of C-Sn bond. In this regard, nineteen DFs from eight different classes of DFT with two effective core potential basis sets (LANL2DZ and SDD) and two Karlsruhe basis sets (def2-SVP and def2-TZVP) are selected for the BDE calcn. of C-Sn bond. Ten structurally diverse organotin compds. with exptl. known BDE of C-Sn bond are selected from the literature. The statistical [root mean square deviation (RMSD), std. deviation (SD), Pearson's correlation (R) and mean abs. error (MAE)] results are obtained by the comparison of theor. data with the exptl. BDE values of C-Sn bond of selected organotin compds. Among all DFT classes, GGA-D class is a batter class and BLYP-D3 functional of this class is selected as the best functional for homolytic bond dissocn. energy (BDE) calcn. of C-Sn bond. This functional with SDD basis set shows remarkable performance in reproducing the BDE of C-Sn bond with more accuracy. The SD, RMSD, R and MAE are 4.11 kcal mol-1 is 3.9 kcal mol-1 is 0.963 and -0.01 kcal mol-1, resp.

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    Kosar, N.; Mahmood, T.; Ayub, K. Role of Dispersion Corrected Hybrid GGA Class in Accurately Calculating the Bond Dissociation Energy of Carbon Halogen Bond: A Benchmark Study. J. Mol. Struct. 2017, 1150, 447– 458,  DOI: 10.1016/j.molstruc.2017.08.104

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    52

    Role of dispersion corrected hybrid GGA class in accurately calculating the bond dissociation energy of carbon halogen bond: A benchmark study

    Kosar, Naveen; Mahmood, Tariq; Ayub, Khurshid

    Journal of Molecular Structure (2017), 1150 (), 447-458CODEN: JMOSB4; ISSN:0022-2860. (Elsevier B.V.)

    Benchmark study has been carried out to find a cost effective and accurate method for bond dissocn. energy (BDE) of carbon halogen (C-X) bond. BDE of C-X bond plays a vital role in chem. reactions, particularly for kinetic barrier and thermochem. etc. The compds. with C-X bond used for the benchmark study are important reactants in org., inorg. and bioorg. chem. Exptl. data of C-X bond dissocn. energy is compared with theor. results. The statistical anal. tools such as root mean square deviation (RMSD), std. deviation (SD), Pearson's correlation (R) and mean abs. error (MAE) are used for comparison. Overall, thirty-one d. functionals from eight different classes of d. functional theory (DFT) along with Pople and Dunning basis sets are evaluated. Among different classes of DFT, the dispersion cor. range sepd. hybrid GGA class along with 6-31G(d), 6-311G(d), aug-cc-pVDZ and aug-cc-pVTZ basis sets performed best for bond dissocn. energy calcn. of C-X bond. The ωB97XD showed the best performance with less deviations (RMSD, SD), mean abs. error (MAE) and a significant Pearson's correlation (R) when compared to exptl. data. The ωB97XD along with Pople basis set 6-311g(d) has RMSD, SD, R and MAE of 3.14 kcal mol-1, 3.05 kcal mol-1, 0.97 and -1.07 kcal mol-1, resp.

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    Van Voorhis, T.; Head-Gordon, M. Benchmark Variational Coupled Cluster Doubles Results. J. Chem. Phys. 2000, 113, 8873– 8879,  DOI: 10.1063/1.1319643

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    53

    Benchmark variational coupled cluster doubles results

    Van Voorhis, Troy; Head-Gordon, Martin

    Journal of Chemical Physics (2000), 113 (20), 8873-8879CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    We present the first application of the Rayleigh-Ritz variational procedure to the coupled cluster doubles trial function. The variational approach is applied to the potential surface of H4, the double dissocn. of water and the dissocn. of N2, and the results are compared to std. coupled cluster doubles calcns. It is found that the variational approach gives a greatly improved description of strongly correlated systems, where the std. approach is known to fail. Some examn. of the basis set dependence of the results is presented.

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    Mardirossian, N.; Parkhill, J. A.; Head-Gordon, M. Benchmark Results for Empirical Post-GGA Functionals: Difficult Exchange Problems and Independent Tests. Phys. Chem. Chem. Phys. 2011, 13, 19325,  DOI: 10.1039/c1cp21635j

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    54

    Benchmark results for empirical post-GGA functionals: Difficult exchange problems and independent tests

    Mardirossian, Narbe; Parkhill, John A.; Head-Gordon, Martin

    Physical Chemistry Chemical Physics (2011), 13 (43), 19325-19337CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)

    A review. Many of the most promising new d. functionals have improved the treatment of non-local exchange effects with the help of semi-empirical information and more sophisticated recipes for combining Hartree-Fock and local exchange approxns. In order to quantify recent advancements and identify directions for improvement, we have examd. a broad spectrum of test problems. We evaluate the performance of several new hybrid d. functionals (ωB97, ωB97X, ωB97X-D, LRC-ωPBEh, M06, M06-2X, and M06-HF) on a variety of chem. problems, some sensitive to the treatment of exact exchange (which we have hoped to systematically improve) and some which require a balanced treatment of correlation. Since all of the functionals under consideration are parameterized with ground-state thermochem. data, the benchmark aims to det. the applicability of the new d. functionals to cases that have not been considered in the optimization of the semi-empirical parameters. The first class of benchmarks includes the excitation energies of 21 mols. (83 states) primarily from a recent benchmark conducted by Tozer and co-workers, with some addnl. refs. from data made available from the groups of Thiel and Truhlar. We briefly examine the conformational preferences of a small peptide and complete our study with two recently published sets of data that have shown large, systematic errors in simple alkane thermochem. While our results indicate that the more general hybrids currently under development perform well for problems outside of their parameterization and improve over the std. hybrid d. functionals in an essentially systematic way, there is still a significant self-interaction error in the more difficult cases. Functionals based on a range-sepn. of exchange and functionals depending on the kinetic-energy d. both perform comparably, and there is evidence for complementary strengths.

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    Gomes, J.; Zimmerman, P. M.; Head-Gordon, M.; Bell, A. T. Accurate Prediction of Hydrocarbon Interactions with Zeolites Utilizing Improved Exchange-Correlation Functionals and QM/MM Methods: Benchmark Calculations of Adsorption Enthalpies and Application to Ethene Methylation by Methanol. J. Phys. Chem. C 2012, 116, 15406– 15414,  DOI: 10.1021/jp303321s

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    Accurate Prediction of Hydrocarbon Interactions with Zeolites Utilizing Improved Exchange-Correlation Functionals and QM/MM Methods: Benchmark Calculations of Adsorption Enthalpies and Application to Ethene Methylation by Methanol

    Gomes, Joseph; Zimmerman, Paul M.; Head-Gordon, Martin; Bell, Alexis T.

    Journal of Physical Chemistry C (2012), 116 (29), 15406-15414CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)

    The adsorption enthalpy of light hydrocarbon mols. in both acidic and neutral zeolite MFI has been investigated with a range of computational methods. The role of cluster model size and d. functional theory methodol. is examd. by comparison with high quality ab initio wave function theory MP2 results and exptl. detd. heats of adsorption. The commonly applied B3LYP functional performs poorly in benchmark studies due to an inadequate description of intermol. interactions. The functionals ωB97X-D and M06-2X predict adsorption enthalpies consistent with exptl. values over three classes of adsorbates. A hybrid quantum mechanics/mol. mechanics (QM/MM) method is required to converge calcd. thermochem. properties with respect to cluster model size in a manner that is computationally efficient. The accuracy of both QM and QM/MM methods is highly sensitive to choice of level of theory and cluster size, requiring the use of large basis sets, large cluster models, and a d. functional capable of capturing intermol. interactions for achieving the desired chem. accuracy of 2 kcal/mol with respect to exptl. detd. adsorption enthalpies and activation barriers. The computational effort for performing QM/MM simulations is considerably lower than that of similar quality QM results, and allows for the chem. accurate simulation of chem. reactions occurring in zeolites in a manner that is computationally cost efficient without sacrificing accuracy. The resulting QM/MM procedure is applied to study the reaction of ethene methylation by methanol.

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