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Basis Set Recommendations for DFT Calculations of Gas-Phase Optical Rotation at Different Wavelengths

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† Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Odense, Denmark
‡ Department of Chemistry, Aarhus University, Aarhus, Denmark
*E-mail: [email protected]
Cite this: J. Chem. Theory Comput. 2012, 8, 11, 4425–4433
Publication Date (Web):August 24, 2012
https://doi.org/10.1021/ct300359s
Copyright © 2012 American Chemical Society
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Abstract

Even for pure substances, the deduction of the absolute configuration is not always straightforward since there is no direct link between the magnitude and sign of the optical rotation and the absolute configuration. It would be very useful to use computations of the optical rotation to link experimentally measured optical rotations to an absolute configuration. Such electronic structure calculations of the optical rotation typically employ regular energy optimized basis sets from wave function theory, and especially the aug-cc-pVDZ basis set has been popular. Here, we have carried out extrapolation of the optical rotation to the basis set limits for nine small or medium sized molecules, using basis sets developed specifically for DFT and magnetic properties (aug-pcS-n series). We suggest that assignment of absolute configuration by comparisons between theoretical and experimental optical rotations may be improved by employing different wavelengths, and accordingly the optical rotation at two wavelengths (589.3 and 355.0 nm) has been investigated. Several fitting schemes were used to estimate the optical rotations at the basis set limit. It was found that use of the aug-cc-pVDZ basis set often leads to results that deviate significantly form the basis set limit results, especially at 355.0 nm but also at 589.3 nm. The double-ζ aug-pcS-1 basis set usually provides results which are closer to the limiting values. The basis set requirements are generally more severe at 355.0 nm, where also the aug-cc-pVTZ and 6-311++G(3fd,3dp) basis sets show significant deviations from the basis set limit results, while the aug-pcS-2 basis set always leads to results within an acceptable deviation.

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Table 1: Statistics over optical rotation calculations for molecules 1–6. Table 2: Results with the modified aug-pcS-3′ basis set versus the original aug-pcS-3 basis set (B3LYP). Table 3: Results with the modified aug-pcS-3′ basis set versus the original aug-pcS-3 basis set (CAM-B3LYP). Table 4: Number of basis set functions for molecules 1–9 with aug-cc-pVXZ and aug-pcS-n basis sets. Figures 1–6: Convergence of aug-cc-pVXZ basis sets versus aug-pcS-n. This material is available free of charge via the Internet at http://pubs.acs.org.

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  2. Ty Balduf, Marco Caricato. Helical Chains of Diatomic Molecules as a Model for Solid-State Optical Rotation. The Journal of Physical Chemistry C 2019, 123 (7) , 4329-4340. https://doi.org/10.1021/acs.jpcc.8b12084
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  10. Ramiro S. Galeano Carrano, Patricio F. Provasi, Marta B. Ferraro, Ibon Alkorta, José Elguero, Stephan P. A. Sauer. A Density Functional Theory Study of Optical Rotation in Some Aziridine and Oxirane Derivatives. ChemPhysChem 2021, 22 (8) , 764-774. https://doi.org/10.1002/cphc.202001010
  11. Jia-Min Lu, Bei-Bei Yang, Li Li. Specific Optical Rotation and Absolute Configuration of Flexible Molecules Containing a 2-Methylbutyl Residue. European Journal of Organic Chemistry 2020, 2020 (30) , 4768-4774. https://doi.org/10.1002/ejoc.202000736
  12. Xing Liu, Jinlong Yang, Zhihao Geng, Hongzhi Jia. Simultaneous measurement of optical rotation dispersion and absorption spectra for chiral substances. Chirality 2020, 32 (8) , 1072-1079. https://doi.org/10.1002/chir.23233
  13. Monika Srebro-Hooper, Jochen Autschbach. Calculating Natural Optical Activity of Molecules from First Principles. Annual Review of Physical Chemistry 2017, 68 (1) , 399-420. https://doi.org/10.1146/annurev-physchem-052516-044827
  14. Balazs Nagy, Frank Jensen. Basis Sets in Quantum Chemistry. 2017,,, 93-149. https://doi.org/10.1002/9781119356059.ch3
  15. F. Reinscheid, U.M. Reinscheid. Stereochemical analysis of (+)-limonene using theoretical and experimental NMR and chiroptical data. Journal of Molecular Structure 2016, 1106 , 141-153. https://doi.org/10.1016/j.molstruc.2015.10.061
  16. Francisco E. Jorge, Amanda Z. de Oliveira, Thiago P. Silva. CAM-B3LYP optical rotations at different wavelengths: Comparison with CCSD results. International Journal of Quantum Chemistry 2016, 116 (1) , 21-26. https://doi.org/10.1002/qua.25015
  17. Angelika Baranowska-Łączkowska, Krzysztof Z. Łączkowski, Christian Henriksen, Berta Fernández, Marta Kozak, Sylwia Zielińska. New basis set for the prediction of the specific rotation in flexible biological molecules. RSC Advances 2016, 6 (24) , 19897-19902. https://doi.org/10.1039/C5RA20186A
  18. Franco Egidi, Ivan Carnimeo, Chiara Cappelli. Optical rotatory dispersion of methyloxirane in aqueous solution: assessing the performance of density functional theory in combination with a fully polarizable QM/MM/PCM approach. Optical Materials Express 2015, 5 (1) , 196. https://doi.org/10.1364/OME.5.000196
  19. Morten N. Pedersen, Erik D. Hedegård, Jacob Kongsted. Basis set error estimation for DFT calculations of electronic g-tensors for transition metal complexes. Journal of Computational Chemistry 2014, 35 (25) , 1809-1814. https://doi.org/10.1002/jcc.23688
  20. James K. Harper, Robbie J. Iuliucci. C-13 Chemical-Shift Tensors in Organic Materials. 2014,,, 1-37. https://doi.org/10.1002/9780470027318.a9295
  21. Bruno A. França, Clarissa O. da Silva. Specific rotation of monosaccharides: a global property bringing local information. Physical Chemistry Chemical Physics 2014, 16 (26) , 13096. https://doi.org/10.1039/c4cp01316f
  22. Angelika Baranowska-Łączkowska, Krzysztof Z. Łączkowski. The ORP basis set designed for optical rotation calculations. Journal of Computational Chemistry 2013, 34 (23) , 2006-2013. https://doi.org/10.1002/jcc.23347

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