Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Interplay between Intra- and Intermolecular Charge Transfer in the Optical Excitations of J-Aggregates

Cite this: J. Phys. Chem. C 2019, 123, 11, 6831–6838
Publication Date (Web):February 25, 2019
https://doi.org/10.1021/acs.jpcc.8b11709

Copyright © 2019 American Chemical Society. This publication is licensed under these Terms of Use.

  • Open Access

Article Views

2641

Altmetric

-

Citations

LEARN ABOUT THESE METRICS
PDF (2 MB)
Supporting Info (1)»

Abstract

In a first-principles study based on density functional theory and many-body perturbation theory, we address the interplay between intra- and intermolecular interactions in a J-aggregate formed by push–pull organic dyes by investigating its electronic and optical properties. We find that the most intense excitation dominating the spectral onset of the aggregate, i.e., the J-band, exhibits a combination of intramolecular charge transfer, coming from the push–pull character of the constituting dyes, and intermolecular charge transfer, due to the dense molecular packing. We also show the presence of a pure intermolecular charge-transfer excitation within the J-band, which is expected to play a relevant role in the emission properties of the J-aggregate. Our results shed light on the microscopic character of optical excitations of J-aggregates and offer new perspectives to further understand the nature of collective excitations in organic semiconductors.

Introduction

ARTICLE SECTIONS
Jump To

J-aggregates are a special class of molecular crystals with enhanced light–matter interaction properties. (1−5) Their optical spectra are dominated by a very strong and narrow peak at the onset—the so-called J-band—which appears at lower energy with respect to the isolated molecular constituents. (6−10) This peculiar feature emerges as a collective effect of the monomers in the aggregated phase and is typically explained in terms of coherent intermolecular dipole coupling. (6,8,9,11,12) The microscopic nature and the fundamental mechanisms that give rise to the J-band are still debated. (6) The situation is even more complex in the case of J-aggregates formed by polar molecules like push–pull organic dyes. In this case, intramolecular charge-transfer (CT) adds up to the aforementioned intermolecular interactions that are responsible for the formation of the J-band. An example of this kind of system is the J-aggregate formed by the organic chromophore 4-(N,N-dimethyl-amino)-4-(2,3,5,6-tetra-fluorostyryl)-stilbene (C24H19F4N), which has been recently proposed and synthesized by Botta et al. (13) Some of the authors have recently investigated this J-aggregate by means of time-dependent density functional theory (TDDFT) showing that its optical behavior cannot be deduced by considering only its isolated components due to the intrinsically supramolecular nature of its optical response. (14) On the other hand, the character of the excitations forming the J-band and the interplay between inter- and intramolecular interactions still need to be addressed. This issue is relevant in the broader context of the electronic structure characterization of molecular crystals. Even in the case of nonpolar molecules, the discussion regarding the nature of optical excitations in organic semiconductors (15−19) is still ongoing. Both localized Frenkel excitons and delocalized intermolecular excitations can appear at the spectral onset of organic semiconductors: Their relative energetic position has been rationalized in terms of intermolecular interactions and wave-function overlap. (19) Identifying the character of the lowest-energy excitations in molecular crystals is particularly relevant to interpret phenomena like multiple exciton generation and singlet fission that have been recently observed in these systems (20−32) and that promise a breakthrough in view of optoelectronic applications. Addressing this question from a theoretical perspective requires a high-level methodology that incorporates a reliable description of the electronic structure and excitations including electron–electron and electron–hole (e–h) correlation effects.
Many-body perturbation theory (MBPT), based on the GW approximation and the solution of the Bethe–Salpeter equation (BSE), is the state-of-the-art approach to investigate optical excitations in crystalline materials. In the last two decades, it has been successfully applied also to molecular systems, providing unprecedented understanding on the character of the excitations therein. (15−19,33−39) Many of these studies are focused on oligoacenes, (15,16,19,35) which have drawn particular attention since the last years of the past century for their appealing optoelectronic and transport properties. (40−47) The first-principles works cited above have revealed that the low-energy excitations in these materials exhibit a remarkable excitonic character, with binding energies of the order of a few hundreds of milli-electron volts and an intermixed Frenkel-like and intermolecular charge-transfer character. Intermolecular interactions generally play a decisive role in the optical properties of a variety of molecular aggregates. (48,49) For example, in azobenzene-functionalized self-assembled monolayers, intermolecular interactions impact strongly on light absorption and excitonic coupling, and hence critically influence the photoisomerization process. (50−53) In these systems, intermolecular coupling and packing effects have been shown to be crucial also in core excitations. (54)
In this work, we adopt the formalism of MBPT to investigate the nature of the excitations in a J-aggregate formed by C24H19F4N dyes (Figure 1), devoting specific attention to the interplay between intra- and intermolecular charge transfer. MBPT calculations are carried out on top of density functional theory (DFT) on the J-aggregate and, for comparison, also on its isolated molecular unit. With the analysis of the quasi-particle (QP) electronic structure and the optical absorption spectra including excitonic effects, we characterize the excited states of this J-aggregate with unprecedented insight. Specifically, we focus on two excited states with different characters appearing within the J-band: the first one gives rise to the main peak of the J-band and manifests a mixed intra- and intermolecular charge-transfer nature; the second one is a very weak excited state possessing a dominant intermolecular CT behavior. This analysis demonstrates how the interplay between intra and intermolecular charge transfer determines the optical properties in a molecular J-aggregate and contributes to the more general understanding of the nature of collective excitations in molecular crystals.

Figure 1

Figure 1. (a) Push–pull organic dye 4-(N,N-dimethyl-amino)-4-(2,3,5,6-tetra-fluorostyryl)-stilbene (C24H19F4N) and its J-aggregate viewed (b) from the ac plane and (c) from the ab plane, with the lattice vectors marked in red; crystallographic structure from CCDC no. 961738 and ref (13). (d) Brillouin zone (BZ) associated with the unit cell of the J-aggregate with the reciprocal lattice vectors indicated in blue, the high-symmetry points highlighted in red, and the path chosen for the band structure plot marked in green.

Methods

ARTICLE SECTIONS
Jump To

Theoretical Background

This study is based on DFT (55,56) and MBPT (the GW approximation and the Bethe–Salpeter equation). (57−59) The workflow adopted to calculate the electronic and optical properties proceeds through three steps: First, a DFT calculation is performed to compute Kohn–Sham (KS) single-particle energies and wave functions as a basis in the successive steps; next, the quasi-particle correction to the KS energies is calculated through a single-shot GW calculation; (57,58,60) the Bethe–Salpeter equation is solved to obtain optical absorption spectra together with excitonic eigenfunctions and eigenenergies. (57) This approach ensures state-of-the-art accuracy methods in the calculation of excited-state properties and, concomitantly, a quantitative insight into the character of the excitations.
In solving the BSE, we adopt the Tamm–Dancoff approximation (TDA) (57) consisting in diagonalizing an effective excitonic Hamiltonian
(1)
where the index v(c) indicates valence (conduction) bands, k and k′ are wave vectors in the Brillouin zone (BZ), and a(a) and b(b) are creation (annihilation) operators for electrons and holes, respectively. The quasi-particle energies ϵck and ϵvk are obtained from the GW calculation. The matrix elements of , which is the short-range unscreened Coulomb interaction, and of W, the statically screened Coulomb interaction, represent the exchange and direct part of the BSE Hamiltonian of eq 1 and are expressed as vckvck = ⟨ck, vk′||vk, ck′⟩ and Wvckvck = ⟨ck, vk′|W|ck′, vk⟩, respectively. The latter takes into account the screened electron–hole interaction (i.e., excitonic effects), while the former is responsible for crystal local-field effects (the factor 2 derives from spin summation in the singlet channel). Note that the potential is a modified Coulomb interaction defined as the bare Coulomb interaction without the long-range (i.e., macroscopic) contribution (i.e., limq→0G=0(q) = 0 in reciprocal space). (61) To quantify local field effects (LFEs) for a certain excited eigenstate |λ⟩ of the excitonic Hamiltonian (eq 1) with excitation energy Eλ, we define the e–h exchange energy , where Avckλ are the BSE coefficients of the eigenstate |λ⟩. When the total excitation energy Eλ is below the QP gap, i.e., EλEGWgap < 0, the excited state |λ> is considered a bound exciton with a binding energy defined as Eb = EGWgapEλ, which physically represents the energy required to separate a bound electron–hole pair into a free electron and a free hole.

Computational Details

The unit cell of the bulk J-aggregate crystal, composed of 192 atoms, corresponding to 4 nonequivalent push–pull molecules, has been taken from the experimental X-ray structure available in the CCDC no. 961738 (for more details, see also the Supporting Information (SI) of ref (13)) without any further relaxation. As previously shown in the case of the pentacene crystal, (16) the optical properties of organic semiconductors are rather insensitive to the optimization of the internal geometry. Moreover, the experimental X-ray structure already takes into account all of the supramolecular effects (e.g., van der Waals, π-stacking, hydrogen bonds, etc.), which determine the relative orientation and the packing of the molecules, is a reliable starting point for our calculations.
DFT calculations of the J-aggregate were performed with the plane-wave code Quantum Espresso (62) by using the semilocal Perdew–Burke–Ernzerhof (PBE) (63) exchange–correlation (xc) functional and treating core electrons with a norm conserving pseudopotential. (64) The plane-wave cutoff for the Kohn–Sham (KS) wave functions (density) was fixed to 40 Ry (160 Ry), and the convergence criterion on the total energy was fixed to 10–8 Ry. The mean residual force per atom is 0.01 Ry/bohr due to nonequilibrium C–H bond lengths, which are however not expected to alter the electronic structure of the system and the essence of our results. GW and BSE calculations were performed using the plane-wave code Yambo. (65) QP corrections were calculated by single-shot GW (i.e., perturbative G0W0) and adopting the Godby–Needs plasmon pole approximation (GN-PPA) model (66) to approximate the frequency dependency of the inverse dielectric function. The GN-PPA is considered a reliable approach for different kinds of bulk systems for which it yields results comparable to the more computationally demanding contour deformation approach. (67−69) Since the QP corrections obtained from G0W0 were almost constant for all of the KS states around the gap, in building the BSE Hamiltonian (eq 1), we applied a scissors plus stretching correction for all of the energies within the irreducible BZ by linear fitting of the QP-corrected values from G0W0 (scissors operator of 1.73 eV and stretching factors Sv = 1.258 and Sc = 1.216 for the occupied and unoccupied states, respectively). The QP gap of the J-aggregate obtained from G0W0 was checked against the one obtained with eigenvalue-only self-consistent GW calculations. The difference between the band gaps obtained with these two methods turned out to be in the order of 160 meV (see Section 2 of the Supporting Information (SI)). The BSE Hamiltonian of the J-aggregate was evaluated and diagonalized within the Tamm–Dancoff approximation using an e–h basis composed of 27 occupied and 34 unoccupied states and a 5 × 3 × 2 k-point grid to sample the BZ. The final absorption spectrum of the bulk crystal was obtained by averaging the spectra computed for three orthogonal electric field polarizations (i.e., along a, b axes and along the component of the c axis perpendicular to the ab plane in Figure 1).
To treat the gas-phase push–pull molecule at the same level of theory as the J-aggregate, we computed the electronic and optical properties for the monomer as extracted from the J-aggregate without any further relaxation. In Section 1 of the SI, we show for the isolated gas-phase monomer that the main effect of the minimization of interatomic forces is to blue-shift the main absorption peak by a few hundreds of milli-electron volts without changing its character. To investigate the electronic and optical properties of the gas-phase push–pull dye, we used MOLGW, (70) a code that implements DFT and MBPT using localized basis orbitals, which are computationally more suited and efficient for isolated systems compared to plane waves. These DFT calculations were carried out using the PBE functional, cc-PVTZ basis set, and a full-electron treatment with frozen-core approximation and total energy convergence precision fixed to 10–8 Ry. The QP correction was computed by an eigenvalue-only self-consistent GW calculation to minimize the dependence on the approximation for the xc functional used in the DFT starting point. (71) To calculate the correlation part of the self-energy, the MOLGW code adopts an analytical expression exploiting the spectral decomposition of the screened Coulomb potential and the residue theorem. (72) The following BSE step was solved in the TDA over a transition space of 50 occupied and 100 unoccupied orbitals. Additional information about the effects of different approximations and codes adopted in these calculations is reported in the SI.

Results and Discussion

ARTICLE SECTIONS
Jump To

We start our analysis by inspecting the electronic structure of the isolated push–pull dye (Figure 1a) and of its J-aggregate (Figure 1b–d). In Figure 2a, the quasi-particle energy levels of the isolated organic dye are shown, together with the isosurface plots of the frontier molecular orbitals (MOs). The dimethylamino (push) and fluorinated ring (pull) groups at the opposite ends of the π-conjugated chromophore are responsible for the polarization on the frontier orbitals and the intrinsic dipole. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are mostly localized on the electron-donating (push) and electron-withdrawing (pull) sides of the molecule, respectively. The QP band structure shown in Figure 2b exhibits a direct gap of 3.2 eV at the Y point, which is more than twice as large as the corresponding DFT (PBE) value of 1.48 eV and is half the QP gap of the isolated molecule, which is 5.66 eV in Figure 2a. The QP correction manifests itself as an almost rigid shift of 1.7 eV for all the conduction bands. This behavior is consistent with that of other organic crystals like pentacene and polythiophene. (18,73) As expected for molecular crystals, (15,16,39,74) the band dispersion is very limited and quite anisotropic: bands are almost flat along those directions in which intermolecular interactions are negligible and the wave-function overlap is hence minimized.

Figure 2

Figure 2. (a) GW energy levels (HOMO level set to zero) and frontier molecular orbitals of the isolated push–pull dye. The isovalues are fixed at 0.04 bohr–3/2. (b) Band structure of the J-aggregate computed from DFT (gray) and one-shot GW (red), where in the latter, a scissors plus stretching has been applied to the DFT energy levels. The Fermi energy is set to zero at the GW valence band maximum (VBM).

Conversely, along the π-stacking directions (e.g., along the Z−Γ−Y path in the BZ), intermolecular interactions are enhanced. As a result, bands are slightly more dispersive and band splitting is observed. Due to the presence of four inequivalent molecules in the unit cell, the bands close to the gap, which exhibit π–π* character, are almost degenerate. In Figure 3, the square moduli of the wave functions at the valence band maximum (VBM) and at the conduction band minimum (CBM) at the high-symmetry point Y are reported. The localized character of the frontier MOs found in the isolated push–pull dye is preserved also in the J-aggregate: The KS states corresponding to the VBM and CBM are mostly localized on the push and pull ends of each monomer, respectively. Figure 4 displays the optical absorption spectra of the isolated push–pull dye in the gas phase (Figure 3a) and of its J-aggregate (Figure 3b). In these plots, the red bars mark the analyzed excited-states. In Tables 1 and 2, we report information about the analyzed excited states for the monomer and the J-aggregate, respectively. The red shift of the principal peak of the J-aggregate with respect to the one of the single molecule amounts to 0.39 eV. This result is in better agreement with the experimental value of 0.48 eV, (13) compared to the outcome of TDDFT calculations with a semilocal xc-functional (14) (0.11 eV). The BSE results reveal also a rich excitonic structure underneath the J-band, which turns out to be composed of several transitions not shown in Figure 4b. Most of these excitations appear below the QP gap at 3.2 eV, and their binding energies do not exceed 0.4 eV, in line with the values reported for conjugated polymers (17,75−78) and slightly smaller than those of crystalline pentacene (0.5 eV), (16,19) picene (0.7 eV), (19) and antracene (0.8 eV). (15)

Figure 3

Figure 3. Isosurfaces of the squared modulus of the KS wave functions of the (a) valence band maximum and (b) conduction band minimum of the J-aggregate computed at the high-symmetry point Y. Isovalues fixed at 0.001 bohr–3.

Figure 4

Figure 4. Absorption spectra of (a) the push–pull dye in the gas phase and (b) in the J-aggregate. The excited states analyzed in the text (M, J, JCT) are marked by red bars with height representative of the relative oscillator strengths. The absorption in both BSE spectra is normalized with respect to the maximum value in the examined energy window. In (b), the absorption spectrum calculated from the independent quasi-particle approximation is also shown (gray-shaded area). All absorption spectra include a Lorentzian line width of 200 meV.

Table 1. Energy and Composition of the First Excited State of the Push–Pull Monomer C24H19F4N, Including the Associated Transition Energy and Weight Given by the Square of the BSE Coefficient
excited state energy (eV)occupied levelunoccupied levelϵcQP – ϵvQP (eV)weight |Acvλ|2
EM = 3.39HOMOLUMO5.730.83
Table 2. Energy and Composition of the J and JCT Excitations of the J-Aggregate, Including the Associated Transition Energy, the Associated k-Point in the Brillouin Zone Expressed in Reciprocal Crystal Units (RCUs), and the Weight Given by the Square of the BSE Coefficienta
excited state energy (eV)occupied bandunoccupied bandk-point (RCU)ϵckQP – ϵvkQP (eV)weight |Acvkλ|2 × 10
EJ = 3VBM – 2CBM + 1(0.4, 0, −0.5)3.340.59
VBM – 2CBM + 1(−0.4, 0, 0.5)3.340.56
VBM – 3CBM(0.4, 0, 0)3.350.54
VBM – 3CBM(−0.4, 0, 0)3.350.52
VBM – 2CBM + 1(0.4, 0, 0)3.330.29
VBM – 3CBM(0.4, 0, −0.5)3.340.29
VBM – 3CBM(−0.4, 0, 0.5)3.340.26
VBM – 2CBM + 1(−0.4, 0, 0)3.330.26
ECTJ = 2.89VBMCBM + 1(−0.2, 0, 0.5)3.290.47
VBMCBM + 1(−0.2, 0, 0)3.280.41
VBMCBM + 1(0.2, 0, −0.5)3.290.40
VBM – 1CBM(−0.2, 0, 0)3.310.37
VBMCBM + 1(0.2, 0, 0)3.280.36
VBM – 1CBM(0.2, 0, 0)3.310.32
VBM – 1CBM(−0.2, 0, 0.5)3.290.26
VBM – 1CBM(−0.4, 0, 0.5)3.230.24
VBMCBM + 1(−0.4, 0, 0)3.220.23
VBM – 1CBM(0.2, 0, −0.5)3.290.23
a

Only weights larger than 2% are reported.

In the following, we focus on two representative excited states within the J-band: the first one labeled as J, at 3 eV, corresponding to the J-band peak; the second one labeled as JCT, at 2.89 eV, which has a very low oscillator strength and represents a paradigmatic example of several intermolecular charge-transfer excited states within the J-band. Both excitations are analyzed in Figure 5 in terms of their excitonic wave functions and transition densities. Information about additional excited states of interest for the J-aggregate is reported in Section 2 of the SI. In Table 2, the composition of the J excitation is reported, showing that it is mainly formed by transitions between (quasi-)degenerate bands at the valence band top and conduction band bottom, which carry π and π* characters like the HOMO and LUMO of the isolated dye (see Figures 2a and 3). The excitonic probability density of the excitation J (Figure 5a,b) reveals its intermixed intramolecular charge transfer as well as intermolecular charge transfer between nearest-neighboring molecules. Having fixed the position of the hole on the push side (i.e., the dimethylamino group) of one molecule in the unit cell, the electron is found on the pull part (i.e., the fluorinated ring) of the same molecule and of its nearest neighbors. By inspecting Figure 5a,b, the electron distribution is also delocalized around neighboring molecules along the π-stacking direction (i.e., the ab plane), where the dispersion is more pronounced because of the enhanced wave-function overlap. The intermolecular character of this excitation is therefore due to the π-interactions in the molecular packing direction, in analogy with the excitons of organic crystals formed by nonpolar molecules. (16,17,79,80) On the other hand, the intramolecular CT nature of the J excitation is inherited from the polarized character of contributing electronic states, in analogy with the MOs of the push–pull molecules constituting the J-aggregate. The transition density of J shown in Figure 5c offers complementary information to the exciton wave function in terms of the spatial distribution of the excitation and the orientation of the molecular transition dipole moments. Since they are coherently aligned and in phase with respect to each other, the excitation J is associated with an induced charge density mainly displaced along the long crystal axis within the ac plane (see Figure 1b). It is also worth noting that, by visual inspection, the transition density shown in Figure 5c does not completely sum to zero within a single monomer unit, as the positive (red) and negative (blue) charge blocks are not present in equal amount. This suggests that there could be a partial intermolecular CT mechanism that has been highlighted above in the analysis of the exciton wave function of Figure 1b. This result has similarities with that obtained for pentacene molecular crystals, (16,19) where exciton delocalization on neighboring molecules also appears. However, as opposed to pentacene, the J-aggregate considered here is composed of polar push–pull molecules: the intrinsic dipole strongly polarizes the frontier MOs and thus reduces the spatial overlap between electron and hole.
The very weak excitation JCT, at slightly lower energy compared to J (see Figure 4b), has a different nature. As shown in Figure 5d–f by the exciton wave function and the transition density, this excitation has a pure intermolecular CT character, with the electron and the hole localized on different neighboring molecules. The slightly larger binding energy of JCT (Eb = 0.32 eV) compared to J (Eb = 0.21 eV) is consistent with its enhanced spatial localization (Figure 5d,e), while the reduced wave-function overlap between the hole and the electron components is consistent with the very weak oscillator strength. Such a CT excitation is associated with lower electron–hole recombination rates and enhanced electron–hole dissociation probability compared to excitons with more pronounced intramolecular character. (81) The transition density associated with JCT (Figure 5c) confirms and complements this picture: neighboring monomers are almost completely depleted of positive and negative charges, respectively, meaning that intermolecular CT is the dominant mechanism here. It is worth mentioning that the character and the microscopic features of excited states, such as JCT, cannot be captured by simple models based on transition dipoles coupling (e.g., the Kasha’s model (11)) but need an advanced first-principles description as provided in this work.

Figure 5

Figure 5. (a, b, d, e) Exciton probability density with fixed hole position (red dot), defined as |Ψλ(re, h)|2 = |⟨λ|Ψ(re)Ψ(h)|0⟩|2 = |∑cvkAvckλφck(revk*(h)|2, where Ψλ(re, h) is the exciton two-body wave function, h (re) is the hole (electron) position, Avckλ is the BSE coefficient for the excited states λ = J, JCT of the J-aggregate, and φvkck) is the occupied (unoccupied) KS electronic state with wavevector k in the BZ; views from the ab plane (a, d) and from ac plane (b, e). The exciton plot gives the probability to find the electron at position re with the hole fixed at h. (c, f) Transition density, defined as ρλ(r) = ⟨λ|Ψ(r)Ψ(r)|0⟩ = ∑cvkAvckλφck(rvk*(r), for the excited states λ = J, JCT of the J-aggregate; views from the ac plane. The transition density provides information about the charge spatial displacement associated with the specific excited state λ. Isosurfaces of the exciton wave functions (transition densities) fixed at 10% of their maximum value.

The intra- and intermolecular character of singlet excitations in organic crystals is determined by a competition between the e–h exchange interaction, which is responsible for the LFE, and the screened e–h attraction. (19) While the exchange interaction is quite sensitive to the spatial overlap between occupied and unoccupied electronic states involved in the transition, the direct e–h attraction can be nonvanishing even upon a negligible spatial overlap between occupied and unoccupied states. (19) Here, due to the push–pull character of the constituting dyes, the gap states of the J-aggregate are quite polarized and hence only slightly overlap (see Figures 2a and 3), as opposed, for instance, to pentacene. (19) Hence, we should expect a reduced influence from the LFE to the low-lying excited states of the J-aggregate. To quantify the contribution of the LFE on a given excited state |λ⟩, we use the e–h exchange energy Exλ and its ratio with respect to the total excitation energy xλ = Exλ/Eλ. In the isolated monomer, ExM = 0.76 eV (xM = 0.22), while in the J-aggregate, ExJ = 0.07 eV (xJ = 0.023) and ExJCT = 0.01 eV (xJCT = 0.003). From these values, it is apparent that LFE contribute ∼20% to the first excitation energy of the isolated monomer while they are almost negligible in the J-aggregate (2% for J and 0.3% for JCT). The predominant intermolecular CT character of JCT is related to a weaker e–h exchange interaction with respect to J, where in the latter, the spatial overlap between the electron and the hole is larger (see also Figure 5a,b). The intermolecular CT that characterizes both J and JCT is favored by the close molecular packing (82−84) of the aggregate, which enhances the electron delocalization between neighboring molecules as generally observed in optical excitations of organic crystals. (17,50,53,54,85,86) The reduction of LFE in the J-aggregate compared to the isolated monomer is due to the more homogeneous electron distribution in the crystal.

Conclusions

ARTICLE SECTIONS
Jump To

To summarize, in the framework of MBPT, we have investigated the electronic and optical properties of a J-aggregate formed by the push–pull organic dye C24H19F4N, specifically addressing the interplay between intra- and intermolecular interactions. We have found that the intense J-band dominating the absorption onset is formed by a number of excitations stemming from transitions between the highest occupied and lowest unoccupied bands. The most intense of these excitations exhibits a combination of inter- and intramolecular charge transfers, resulting from the competing effects of dense molecular packing and the push–pull nature of the constituting molecules. The other excitations within the J-band have very weak intensity. Among them, JCT has pronounced intermolecular charge-transfer character. Being at lower energy compared to the most intense excitation in the J-band, this state is expected to play a relevant role in the emission properties of the J-aggregate.
Our analysis demonstrates that the complex mechanisms ruling the optical properties of organic crystalline aggregates cannot be unveiled based solely on simple models, but require a high level of theory that is able to quantitatively address all of the facets of the problem. Many-body perturbation theory is capable of thoroughly capturing the collective effects and providing a robust insight into the excitations of the system. As such, our results offer unprecedented insight into the nature of the excitations of J-aggregates formed by push–pull chromophores and contribute to the further understanding of these materials that are relevant for optoelectronic applications.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b11709.

  • Electronic and optical properties of the isolated push–pull monomer and the J-aggregate (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

ARTICLE SECTIONS
Jump To

  • Corresponding Authors
  • Authors
    • Michele Guerrini - Dipartimento FIM, Università di Modena e Reggio Emilia, 41125 Modena, ItalyCNR Nano Istituto Nanoscienze, Centro S3, 41125 Modena, ItalyDepartment of Physics and IRIS Adlershof, Humboldt-Universität zu Berlin, 12489 Berlin, Germany
    • Arrigo Calzolari - CNR Nano Istituto Nanoscienze, Centro S3, 41125 Modena, ItalyOrcidhttp://orcid.org/0000-0002-0244-7717
    • Stefano Corni - CNR Nano Istituto Nanoscienze, Centro S3, 41125 Modena, ItalyDipartimento di Scienze Chimiche, Università di Padova, 35131 Padova, ItalyOrcidhttp://orcid.org/0000-0001-6707-108X
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

ARTICLE SECTIONS
Jump To

This work was partially funded by the European Union under the ERC grant TAME Plasmons (ERC-CoG-681285), by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)—Projektnummer 182087777—SFB 951 and HE 5866/2-1, and by the EU Centre of Excellence “MaX - Materials Design at the Exascale” (Horizon 2020 EINFRA-5, Grant No. 676598). M.G. acknowledges support from the German Academic Exchange Service (DAAD) and HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme. Computational resources were partly provided by PRACE on the Marconi machine at CINECA and by the High-Performance Computing Center Stuttgart (HLRS).

References

ARTICLE SECTIONS
Jump To

This article references 86 other publications.

  1. 1
    Bricks, J. L.; Slominskii, Y. L.; Panas, I. D.; Demchenko, A. P. Fluorescent J-Aggregates of Cyanine Dyes: Basic Research and Applications Review. Methods Appl. Fluoresc. 2017, 6, 012001  DOI: 10.1088/2050-6120/aa8d0d
  2. 2
    Melnikau, D.; Savateeva, D.; Susha, A. S.; Rogach, A. L.; Rakovich, Y. P. Strong Plasmon-Exciton Coupling in a Hybrid System of Gold Nanostars and J-Aggregates. Nanoscale Res. Lett. 2013, 8, 134  DOI: 10.1186/1556-276X-8-134
  3. 3
    Ferdele, S.; Jose, B.; Foster, R.; Keyes, T. E.; Rice, J. H. Strong Coupling in Porphyrin J-Aggregate Excitons and Plasmons in Nano-Void Arrays. Opt. Mater. 2017, 72, 680684,  DOI: 10.1016/j.optmat.2017.07.018
  4. 4
    Wurtz, G. A.; Evans, P. R.; Hendren, W.; Atkinson, R.; Dickson, W.; Pollard, R. J.; Zayats, A. V.; Harrison, W.; Bower, C. Molecular Plasmonics with Tunable Exciton–Plasmon Coupling Strength in J-Aggregate Hybridized Au Nanorod Assemblies. Nano Lett. 2007, 7, 12971303,  DOI: 10.1021/nl070284m
  5. 5
    Fofang, N. T.; Park, T.-H.; Neumann, O.; Mirin, N. A.; Nordlander, P.; Halas, N. J. Plexcitonic Nanoparticles: Plasmon–Exciton Coupling in Nanoshell–J-Aggregate Complexes. Nano Lett. 2008, 8, 34813487,  DOI: 10.1021/nl8024278
  6. 6
    Egorov, V. V. Theory of the J-Band: From the Frenkel Exciton to Charge Transfer. Phys. Procedia 2009, 2, 223326,  DOI: 10.1016/j.phpro.2009.07.014
  7. 7
    Jelley, E. E. Spectral Absorption and Fluorescence of Dyes in the Molecular State. Nature 1936, 138, 1009,  DOI: 10.1038/1381009a0
  8. 8
    Eisfeld, A.; Briggs, J. S. The J-Band of Organic Dyes: Lineshape and Coherence Length. Chem. Phys. 2002, 281, 6170,  DOI: 10.1016/S0301-0104(02)00594-3
  9. 9
    Eisfeld, A.; Briggs, J. S. The J- and H-Bands of Organic Dye Aggregates. Chem. Phys. 2006, 324, 376384,  DOI: 10.1016/j.chemphys.2005.11.015
  10. 10
    Walczak, P. B.; Eisfeld, A.; Briggs, J. S. Exchange Narrowing of the J Band of Molecular Dye Aggregates. J. Chem. Phys. 2008, 128, 044505  DOI: 10.1063/1.2823730
  11. 11
    Kasha, M. Energy Transfer Mechanisms and the Molecular Exciton Model for Molecular Aggregates. Radiat. Res. 1963, 20, 5570,  DOI: 10.2307/3571331
  12. 12
    Kasha, M.; Rawls, H. R.; Ashraf El-Bayoumi, M. The Exciton Model in Molecular Spectroscopy. Pure Appl. Chem. 1965, 11, 371392,  DOI: 10.1351/pac196511030371
  13. 13
    Botta, C.; Cariati, E.; Cavallo, G.; Dichiarante, V.; Forni, A.; Metrangolo, P.; Pilati, T.; Resnati, G.; Righetto, S.; Terraneo, G. Fluorine-Induced J-Aggregation Enhances Emissive Properties of a New NLO Push-Pull Chromophore. J. Mater. Chem. C 2014, 2, 52755279,  DOI: 10.1039/c4tc00665h
  14. 14
    Guerrini, M.; Calzolari, A.; Corni, S. Solid-State Effects on the Optical Excitation of Push–Pull Molecular J-Aggregates by First-Principles Simulations. ACS Omega 2018, 3, 1048110486,  DOI: 10.1021/acsomega.8b01457
  15. 15
    Hummer, K.; Puschnig, P.; Ambrosch-Draxl, C. Lowest Optical Excitations in Molecular Crystals: Bound Excitons versus Free Electron-Hole Pairs in Anthracene. Phys. Rev. Lett. 2004, 92, 147402  DOI: 10.1103/PhysRevLett.92.147402
  16. 16
    Cocchi, C.; Breuer, T.; Witte, G.; Draxl, C. Polarized Absorbance and Davydov Splitting in Bulk and Thin-Film Pentacene Polymorphs. Phys. Chem. Chem. Phys. 2018, 20, 2972429736,  DOI: 10.1039/C8CP06384B
  17. 17
    Ruini, A.; Caldas, M. J.; Bussi, G.; Molinari, E. Solid State Effects on Exciton States and Optical Properties of PPV. Phys. Rev. Lett. 2002, 88, 206403  DOI: 10.1103/PhysRevLett.88.206403
  18. 18
    Tiago, M. L.; Northrup, J. E.; Louie, S. G. Ab Initio Calculation of the Electronic and Optical Properties of Solid Pentacene. Phys. Rev. B 2003, 67, 115212  DOI: 10.1103/PhysRevB.67.115212
  19. 19
    Cudazzo, P.; Gatti, M.; Rubio, A. Excitons in Molecular Crystals from First-Principles Many-Body Perturbation Theory: Picene versus Pentacene. Phys. Rev. B 2012, 86, 195307  DOI: 10.1103/PhysRevB.86.195307
  20. 20
    Broch, K.; Dieterle, J.; Branchi, F.; Hestand, N. J.; Olivier, Y.; Tamura, H.; Cruz, C.; Nichols, V. M.; Hinderhofer, A.; Beljonne, D. Robust Singlet Fission in Pentacene Thin Films with Tuned Charge Transfer Interactions. Nat. Commun. 2018, 9, 954  DOI: 10.1038/s41467-018-03300-1
  21. 21
    Zeng, T.; Hoffmann, R.; Ananth, N. The Low-Lying Electronic States of Pentacene and Their Roles in Singlet Fission. J. Am. Chem. Soc. 2014, 136, 57555764,  DOI: 10.1021/ja500887a
  22. 22
    Refaely-Abramson, S.; da Jornada, F. H.; Louie, S. G.; Neaton, J. B. Origins of Singlet Fission in Solid Pentacene from an Ab Initio Green’s Function Approach. Phys. Rev. Lett. 2017, 119, 267401  DOI: 10.1103/PhysRevLett.119.267401
  23. 23
    Coto, P. B.; Sharifzadeh, S.; Neaton, J. B.; Thoss, M. Low-Lying Electronic Excited States of Pentacene Oligomers: A Comparative Electronic Structure Study in the Context of Singlet Fission. J. Chem. Theory Comput. 2015, 11, 147156,  DOI: 10.1021/ct500510k
  24. 24
    Beljonne, D.; Yamagata, H.; Brédas, J. L.; Spano, F. C.; Olivier, Y. Charge-Transfer Excitations Steer the Davydov Splitting and Mediate Singlet Exciton Fission in Pentacene. Phys. Rev. Lett. 2013, 110, 226402  DOI: 10.1103/PhysRevLett.110.226402
  25. 25
    Kolata, K.; Breuer, T.; Witte, G.; Chatterjee, S. Molecular Packing Determines Singlet Exciton Fission in Organic Semiconductors. ACS Nano 2014, 8, 73777383,  DOI: 10.1021/nn502544d
  26. 26
    Berkelbach, T. C.; Hybertsen, M. S.; Reichman, D. R. Microscopic Theory of Singlet Exciton Fission. III. Crystalline Pentacene. J. Chem. Phys. 2014, 141, 074705  DOI: 10.1063/1.4892793
  27. 27
    Berkelbach, T. C.; Hybertsen, M. S.; Reichman, D. R. Microscopic Theory of Singlet Exciton Fission. II. Application to Pentacene Dimers and the Role of Superexchange. J. Chem. Phys. 2013, 138, 114103  DOI: 10.1063/1.4794427
  28. 28
    Sharifzadeh, S.; Darancet, P.; Kronik, L.; Neaton, J. B. Low-Energy Charge-Transfer Excitons in Organic Solids from First-Principles: The Case of Pentacene. J. Phys. Chem. Lett. 2013, 4, 21972201,  DOI: 10.1021/jz401069f
  29. 29
    Wilson, M. W. B.; Rao, A.; Ehrler, B.; Friend, R. H. Singlet Exciton Fission in Polycrystalline Pentacene: From Photophysics toward Devices. Acc. Chem. Res. 2013, 46, 13301338,  DOI: 10.1021/ar300345h
  30. 30
    Wilson, M. W. B.; Rao, A.; Clark, J.; Kumar, R. S. S.; Brida, D.; Cerullo, G.; Friend, R. H. Ultrafast Dynamics of Exciton Fission in Polycrystalline Pentacene. J. Am. Chem. Soc. 2011, 133, 1183011833,  DOI: 10.1021/ja201688h
  31. 31
    Zimmerman, P. M.; Bell, F.; Casanova, D.; Head-Gordon, M. Mechanism for Singlet Fission in Pentacene and Tetracene: From Single Exciton to Two Triplets. J. Am. Chem. Soc. 2011, 133, 1994419952,  DOI: 10.1021/ja208431r
  32. 32
    Zimmerman, P. M.; Zhang, Z.; Musgrave, C. B. Singlet Fission in Pentacene through Multi-Exciton Quantum States. Nat. Chem. 2010, 2, 648,  DOI: 10.1038/nchem.694
  33. 33
    Schuster, R.; Knupfer, M.; Berger, H. Exciton Band Structure of Pentacene Molecular Solids: Breakdown of the Frenkel Exciton Model. Phys. Rev. Lett. 2007, 98, 037402  DOI: 10.1103/PhysRevLett.98.037402
  34. 34
    Cudazzo, P.; Sottile, F.; Rubio, A.; Gatti, M. Exciton Dispersion in Molecular Solids. J. Phys.: Condens. Matter 2015, 27, 113204  DOI: 10.1088/0953-8984/27/11/113204
  35. 35
    Hummer, K.; Ambrosch-Draxl, C. Oligoacene Exciton Binding Energies: Their Dependence on Molecular Size. Phys. Rev. B 2005, 71, 081202  DOI: 10.1103/PhysRevB.71.081202
  36. 36
    Bussi, G.; Ruini, A.; Molinari, E.; Caldas, M. J.; Puschnig, P.; Ambrosch-Draxl, C. Interchain Interaction and Davydov Splitting in Polythiophene Crystals: An Ab Initio Approach. Appl. Phys. Lett. 2002, 80, 41184120,  DOI: 10.1063/1.1483905
  37. 37
    Rangel, T.; Berland, K.; Sharifzadeh, S.; Brown-Altvater, F.; Lee, K.; Hyldgaard, P.; Kronik, L.; Neaton, J. B. Structural and Excited-State Properties of Oligoacene Crystals from First Principles. Phys. Rev. B 2016, 93, 115206  DOI: 10.1103/PhysRevB.93.115206
  38. 38
    Sharifzadeh, S.; Biller, A.; Kronik, L.; Neaton, J. B. Quasiparticle and Optical Spectroscopy of the Organic Semiconductors Pentacene and PTCDA from First Principles. Phys. Rev. B 2012, 85, 125307  DOI: 10.1103/PhysRevB.85.125307
  39. 39
    Ambrosch-Draxl, C.; Nabok, D.; Puschnig, P.; Meisenbichler, C. The Role of Polymorphism in Organic Thin Films: Oligoacenes Investigated from First Principles. New J. Phys. 2009, 11, 125010  DOI: 10.1088/1367-2630/11/12/125010
  40. 40
    Nelson, S. F.; Lin, Y.-Y.; Gundlach, D. J.; Jackson, T. N. Temperature-Independent Transport in High-Mobility Pentacene Transistors. Appl. Phys. Lett. 1998, 72, 18541856,  DOI: 10.1063/1.121205
  41. 41
    Lee, J. Y.; Roth, S.; Park, Y. W. Anisotropic Field Effect Mobility in Single Crystal Pentacene. Appl. Phys. Lett. 2006, 88, 252106  DOI: 10.1063/1.2216400
  42. 42
    Takeya, J.; Yamagishi, M.; Tominari, Y.; Hirahara, R.; Nakazawa, Y.; Nishikawa, T.; Kawase, T.; Shimoda, T.; Ogawa, S. Very High-Mobility Organic Single-Crystal Transistors with in-Crystal Conduction Channels. Appl. Phys. Lett. 2007, 90, 102120  DOI: 10.1063/1.2711393
  43. 43
    Dimitrakopoulos, C. D.; Brown, A. R.; Pomp, A. Molecular Beam Deposited Thin Films of Pentacene for Organic Field Effect Transistor Applications. J. Appl. Phys. 1996, 80, 25012508,  DOI: 10.1063/1.363032
  44. 44
    Lin, Y.-Y.; Gundlach, D. I.; Nelson, S. F.; Jackson, T. N. Pentacene-Based Organic Thin-Film Transistors. IEEE Trans. Electron Devices 1997, 44, 13251331,  DOI: 10.1109/16.605476
  45. 45
    Jin, Y.; Rang, Z.; Nathan, M. I.; Ruden, P. P.; Newman, C. R.; Frisbie, C. D. Pentacene Organic Field-Effect Transistor on Metal Substrate with Spin-Coated Smoothing Layer. Appl. Phys. Lett. 2004, 85, 44064408,  DOI: 10.1063/1.1814802
  46. 46
    Yang, S. Y.; Shin, K.; Park, C. E. The Effect of Gate-Dielectric Surface Energy on Pentacene Morphology and Organic Field-Effect Transistor Characteristics. Adv. Funct. Mater. 2005, 15, 18061814,  DOI: 10.1002/adfm.200400486
  47. 47
    Graz, I. M.; Lacour, S. P. Flexible Pentacene Organic Thin Film Transistor Circuits Fabricated Directly onto Elastic Silicone Membranes. Appl. Phys. Lett. 2009, 95, 243305  DOI: 10.1063/1.3265737
  48. 48
    Varghese, S.; Das, S. Role of Molecular Packing in Determining Solid-State Optical Properties of π-Conjugated Materials. J. Phys. Chem. Lett. 2011, 2, 863873,  DOI: 10.1021/jz200099p
  49. 49
    Köhler, A.; Wilson, J. S.; Friend, R. H. Fluorescence and Phosphorescence in Organic Materials. Adv. Mater. 2002, 14, 701707,  DOI: 10.1002/1521-4095(20020517)14:10<701::AID-ADMA701>3.0.CO;2-4
  50. 50
    Benassi, E.; Corni, S. Exciton Transfer of Azobenzene Derivatives in Self-Assembled Monolayers. J. Phys. Chem. C 2013, 117, 2502625041,  DOI: 10.1021/jp405077w
  51. 51
    Utecht, M.; Klamroth, T.; Saalfrank, P. Optical Absorption and Excitonic Coupling in Azobenzenes Forming Self-Assembled Monolayers: A Study Based on Density Functional Theory. Phys. Chem. Chem. Phys. 2011, 13, 2160821614,  DOI: 10.1039/c1cp22793a
  52. 52
    Cocchi, C.; Moldt, T.; Gahl, C.; Weinelt, M.; Draxl, C. Optical Properties of Azobenzene-Functionalized Self-Assembled Monolayers: Intermolecular Coupling and Many-Body Interactions. J. Chem. Phys. 2016, 145, 234701  DOI: 10.1063/1.4971436
  53. 53
    Cocchi, C.; Draxl, C. Understanding the Effects of Packing and Chemical Terminations on the Optical Excitations of Azobenzene-Functionalized Self-Assembled Monolayers. J. Phys.: Condens. Matter 2017, 29, 394005  DOI: 10.1088/1361-648X/aa7ca7
  54. 54
    Cocchi, C.; Draxl, C. Bound Excitons and Many-Body Effects in x-Ray Absorption Spectra of Azobenzene-Functionalized Self-Assembled Monolayers. Phys. Rev. B 2015, 92, 205105  DOI: 10.1103/PhysRevB.92.205105
  55. 55
    Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas. Phys. Rev. 1964, 136, B864B871,  DOI: 10.1103/PhysRev.136.B864
  56. 56
    Kohn, W.; Sham, L. J. Self-Consistent Equations Including Exchange and Correlation Effects. Phys. Rev. 1965, 140, A1133A1138,  DOI: 10.1103/PhysRev.140.A1133
  57. 57
    Onida, G.; Reining, L.; Rubio, A. Electronic Excitations: Density-Functional versus Many-Body Green’s-Function Approaches. Rev. Mod. Phys. 2002, 74, 601659,  DOI: 10.1103/RevModPhys.74.601
  58. 58
    Hedin, L. New Method for Calculating the One-Particle Green’s Function with Application to the Electron-Gas-Problem. Phys. Rev. 1965, 139, A796,  DOI: 10.1103/PhysRev.139.A796
  59. 59
    Strinati, G. Application of the Green’s Functions Method to the Study of the Optical Properties of Semiconductors. La Riv. Nuovo Cimento 1988, 11, 186,  DOI: 10.1007/BF02725962
  60. 60
    Hybertsen, M. S.; Louie, S. G. Electron Correlation in Semiconductors and Insulators: Band Gaps and Quasiparticle Energies. Phys. Rev. B 1986, 34, 53905413,  DOI: 10.1103/PhysRevB.34.5390
  61. 61
    Hanke, W. Dielectric Theory of Elementary Excitations in Crystals. Adv. Phys. 1978, 27, 287341,  DOI: 10.1080/00018737800101384
  62. 62
    Giannozzi, P.; Baroni, S.; Bonini, N.; Calandra, M.; Car, R.; Cavazzoni, C.; Ceresoli, D.; Chiarotti, G. L.; Cococcioni, M.; Dabo, I. QUANTUM ESPRESSO: A Modular and Open-Source Software Project for Quantum Simulations of Materials. J. Phys.: Condens. Matter 2009, 21, 395502  DOI: 10.1088/0953-8984/21/39/395502
  63. 63
    Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 38653868,  DOI: 10.1103/PhysRevLett.77.3865
  64. 64
    Hamann, D. R. Optimized Norm-Conserving Vanderbilt Pseudopotentials. Phys. Rev. B 2013, 88, 085117  DOI: 10.1103/PhysRevB.88.085117
  65. 65
    Marini, A.; Hogan, C.; Grüning, M.; Varsano, D. Yambo: An Ab Initio Tool for Excited State Calculations. Comput. Phys. Commun. 2009, 180, 13921403,  DOI: 10.1016/j.cpc.2009.02.003
  66. 66
    Godby, R. W.; Needs, R. J. Metal-Insulator Transition in Kohn-Sham Theory and Quasiparticle Theory. Phys. Rev. Lett. 1989, 62, 11691172,  DOI: 10.1103/PhysRevLett.62.1169
  67. 67
    Larson, P.; Dvorak, M.; Wu, Z. Role of the Plasmon-Pole Model in the GW Approximation. Phys. Rev. B 2013, 88, 125205  DOI: 10.1103/PhysRevB.88.125205
  68. 68
    Stankovski, M.; Antonius, G.; Waroquiers, D.; Miglio, A.; Dixit, H.; Sankaran, K.; Giantomassi, M.; Gonze, X.; Côté, M.; Rignanese, G.-M. G0W0 Band Gap of ZnO: Effects of Plasmon-Pole Models. Phys. Rev. B 2011, 84, 241201  DOI: 10.1103/PhysRevB.84.241201
  69. 69
    Lebègue, S.; Arnaud, B.; Alouani, M.; Bloechl, P. E. Implementation of an All-Electron GW Approximation Based on the Projector Augmented Wave Method without Plasmon Pole Approximation: Application to Si, SiC, AlAs, InAs, NaH, and KH. Phys. Rev. B 2003, 67, 155208  DOI: 10.1103/PhysRevB.67.155208
  70. 70
    Bruneval, F.; Rangel, T.; Hamed, S. M.; Shao, M.; Yang, C.; Neaton, J. B. MOLGW 1: Many-Body Perturbation Theory Software for Atoms, Molecules, and Clusters. Comput. Phys. Commun. 2016, 208, 149161,  DOI: 10.1016/j.cpc.2016.06.019
  71. 71
    Bruneval, F.; Marques, M. A. L. Benchmarking the Starting Points of the GW Approximation for Molecules. J. Chem. Theory Comput. 2013, 9, 324329,  DOI: 10.1021/ct300835h
  72. 72
    Bruneval, F.; Rangel, T.; Hamed, S. M.; Shao, M.; Yang, C.; Neaton, J. B. MOLGW 1: Many-Body Perturbation Theory Software for Atoms, Molecules, and Clusters. Comput. Phys. Commun. 2016, 208, 149161,  DOI: 10.1016/j.cpc.2016.06.019
  73. 73
    van der Horst, J.; Bobbert, P.; de Jong, P.; Michels, M.; Brocks, G.; Kelly, P. Ab Initio Prediction of the Electronic and Optical Excitations in Polythiophene: Isolated Chains versus Bulk Polymer. Phys. Rev. B 2000, 61, 1581715826,  DOI: 10.1103/PhysRevB.61.15817
  74. 74
    Cocchi, C.; Draxl, C. Optical Spectra from Molecules to Crystals: Insight from Many-Body Perturbation Theory. Phys. Rev. B 2015, 92, 5126,  DOI: 10.1103/PhysRevB.92.205126
  75. 75
    Alvarado, S. F.; Seidler, P. F.; Lidzey, D. G.; Bradley, D. D. C. Direct Determination of the Exciton Binding Energy of Conjugated Polymers Using a Scanning Tunneling Microscope. Phys. Rev. Lett. 1998, 81, 10821085,  DOI: 10.1103/PhysRevLett.81.1082
  76. 76
    Campbell, I. H.; Hagler, T. W.; Smith, D. L.; Ferraris, J. P. Direct Measurement of Conjugated Polymer Electronic Excitation Energies Using Metal/Polymer/Metal Structures. Phys. Rev. Lett. 1996, 76, 19001903,  DOI: 10.1103/PhysRevLett.76.1900
  77. 77
    Barth, S.; Bässler, H. Intrinsic Photoconduction in PPV-Type Conjugated Polymers. Phys. Rev. Lett. 1997, 79, 44454448,  DOI: 10.1103/PhysRevLett.79.4445
  78. 78
    Varsano, D.; Marini, A.; Rubio, A. Optical Saturation Driven by Exciton Confinement in Molecular Chains: A Time-Dependent Density-Functional Theory Approach. Phys. Rev. Lett. 2008, 101, 133002  DOI: 10.1103/PhysRevLett.101.133002
  79. 79
    Cocchi, C.; Prezzi, D.; Ruini, A.; Caldas, M. J.; Molinari, E. Optical Properties and Charge-Transfer Excitations in Edge-Functionalized All-Graphene Nanojunctions. J. Phys. Chem. Lett. 2011, 2, 13151319,  DOI: 10.1021/jz200472a
  80. 80
    Ruini, A. Ab Initio Optical Absorption in Conjugated Polymers: The Role of Dimensionality. Phys. Scr. 2004, T109, 121,  DOI: 10.1238/Physica.Topical.109a00121
  81. 81
    Barford, W. Electronic and Optical Properties of Conjugated Polymers; International Series of Monographs on Physics; OUP: Oxford, 2005.
  82. 82
    Dreuw, A.; Head-Gordon, M. Single-Reference Ab Initio Methods for the Calculation of Excited States of Large Molecules. Chem. Rev. 2005, 105, 40094037,  DOI: 10.1021/cr0505627
  83. 83
    Dreuw, A.; Weisman, J. L.; Head-gordon, M. Long-Range Charge-Transfer Excited States in Time-Dependent Density Functional Theory Require non-local Exchange. J. Chem. Phys. 2003, 119, 2943,  DOI: 10.1063/1.1590951
  84. 84
    Dreuw, A.; Head-Gordon, M. Failure of Time-Dependent Density Functional Theory for Long-Range Charge-Transfer Excited States: The Zincbacteriochlorin–Bacteriochlorin and Bacteriochlorophyll–Spheroidene Complexes. J. Am. Chem. Soc. 2004, 126, 40074016,  DOI: 10.1021/ja039556n
  85. 85
    Hummer, K.; Puschnig, P.; Ambrosch-Draxl, C. Ab Initio Study of Anthracene under High Pressure. Phys. Rev. B 2003, 67, 184105  DOI: 10.1103/PhysRevB.67.184105
  86. 86
    Puschnig, P.; Hummer, K.; Ambrosch-Draxl, C.; Heimel, G.; Oehzelt, M.; Resel, R. Electronic, Optical, and Structural Properties of Oligophenylene Molecular Crystals under High Pressure: An Ab Initio Investigation. Phys. Rev. B 2003, 67, 235321  DOI: 10.1103/PhysRevB.67.235321

Cited By

ARTICLE SECTIONS
Jump To

This article is cited by 20 publications.

  1. Yilin Liu, Zibo Li, Yang Xu, Xia Xu, Jie Zhao, Wei Cui, Junbai Li. Ion-Induced Nanoarchitectonics for Anthraquinone Single Crystals with Enhanced Fluorescence Properties. ACS Applied Materials & Interfaces 2024, 16 (7) , 9436-9442. https://doi.org/10.1021/acsami.3c16293
  2. Holger-Dietrich Saßnick, Fabiana Machado Ferreira De Araujo, Joshua Edzards, Caterina Cocchi. Impact of Ligand Substitution and Metal Node Exchange in the Electronic Properties of Scandium Terephthalate Frameworks. Inorganic Chemistry 2024, 63 (4) , 2098-2108. https://doi.org/10.1021/acs.inorgchem.3c03945
  3. P. Grobas Illobre, M. Marsili, S. Corni, M. Stener, D. Toffoli, E. Coccia. Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms. Journal of Chemical Theory and Computation 2021, 17 (10) , 6314-6329. https://doi.org/10.1021/acs.jctc.1c00211
  4. Louis P. Doctor, Marco Naumann, Frank Ziegs, Bernd Büchner, Alexey Popov, Martin Knupfer. Strong Photophysical Diversity and the Role of Charge Transfer Excitons in Transition Metal Phthalocyanine β-Phases. The Journal of Physical Chemistry C 2021, 125 (22) , 12398-12404. https://doi.org/10.1021/acs.jpcc.1c02654
  5. Daniele Cortecchia, Wojciech Mróz, Giulia Folpini, Tetiana Borzda, Luca Leoncino, Ada Lili Alvarado-Leaños, Emily Mae Speller, Annamaria Petrozza. Layered Perovskite Doping with Eu3+ and β-diketonate Eu3+ Complex. Chemistry of Materials 2021, 33 (7) , 2289-2297. https://doi.org/10.1021/acs.chemmater.0c04097
  6. Malavika Arvind, Claudia E. Tait, Michele Guerrini, Jannis Krumland, Ana M. Valencia, Caterina Cocchi, Ahmed E. Mansour, Norbert Koch, Stephen Barlow, Seth R. Marder, Jan Behrends, Dieter Neher. Quantitative Analysis of Doping-Induced Polarons and Charge-Transfer Complexes of Poly(3-hexylthiophene) in Solution. The Journal of Physical Chemistry B 2020, 124 (35) , 7694-7708. https://doi.org/10.1021/acs.jpcb.0c03517
  7. Michele Guerrini, Arrigo Calzolari, Daniele Varsano, Stefano Corni. Quantifying the Plasmonic Character of Optical Excitations in a Molecular J-Aggregate. Journal of Chemical Theory and Computation 2019, 15 (5) , 3197-3203. https://doi.org/10.1021/acs.jctc.9b00220
  8. Jiaxin Guo, Pan Qi, Yongkang Zhang, Cunlan Guo. Tuning Charge Transport of Oligopeptide Junctions via Interfacial Amino Acids †. Chinese Journal of Chemistry 2023, 41 (17) , 2113-2118. https://doi.org/10.1002/cjoc.202300098
  9. Babak J. Mehrara, Andrea J. Radtke, Gwendalyn J. Randolph, Brianna T. Wachter, Patricia Greenwel, Ilsa I. Rovira, Zorina S. Galis, Selen C. Muratoglu. The emerging importance of lymphatics in health and disease: an NIH workshop report. Journal of Clinical Investigation 2023, 133 (17) https://doi.org/10.1172/JCI171582
  10. Rikitha S Fernandes, Nilanjan Dey. A combinatorial effect of TICT and AIE on bisulfate detection using a pyrenylated charge-transfer luminogen. Materials Research Bulletin 2023, 163 , 112192. https://doi.org/10.1016/j.materresbull.2023.112192
  11. Louis Philip Doctor, Martin Knupfer. Momentum dependence of the spectral weight in late transition metal phthalocyanine β -phases. Organic Electronics 2023, 117 , 106783. https://doi.org/10.1016/j.orgel.2023.106783
  12. Komal Bhardwaj, Samya Naqvi, Saurabh K Saini, Mahesh Kumar, Rachana Kumar. Perylenediimide derivatives with branched imide substituents: Aggregation behaviour and impact on photovoltaic properties. Solar Energy 2022, 246 , 320-330. https://doi.org/10.1016/j.solener.2022.10.012
  13. Claire Tonnelé, Manon Catherin, Michel Giorgi, Gabriel Canard, David Casanova, Frédéric Castet, Elena Zaborova, Frédéric Fages. Optoelectronic properties of a self-assembling rigidly-linked BF2-curcuminoid bichromophore. Dyes and Pigments 2022, 207 , 110677. https://doi.org/10.1016/j.dyepig.2022.110677
  14. Corentin Pigot, Sébastien Péralta, Thanh-Tuân Bui, Malek Nechab, Frédéric Dumur. Push-pull dyes based on Michler's aldehyde: Design and characterization of the optical and electrochemical properties. Dyes and Pigments 2022, 202 , 110278. https://doi.org/10.1016/j.dyepig.2022.110278
  15. Amir Mohammad Rezaei Zangeneh, Ali Farmani, Mohammad Hazhir Mozaffari, Ali Mir. Enhanced sensing of terahertz surface plasmon polaritons in graphene/J-aggregate coupler using FDTD method. Diamond and Related Materials 2022, 125 , 109005. https://doi.org/10.1016/j.diamond.2022.109005
  16. David Dell’Angelo, Mohammad R. Momeni, Shaina Pearson, Farnaz A. Shakib. Modeling energy transfer and absorption spectra in layered metal–organic frameworks based on a Frenkel–Holstein Hamiltonian. The Journal of Chemical Physics 2022, 156 (4) https://doi.org/10.1063/5.0076640
  17. Peng Li, Guojing Xu, Nannan Wang, Bo Guan, Shuiqing Zhu, Penglei Chen, Minghua Liu. 0D, 1D, and 2D Supramolecular Nanoassemblies of a Porphyrin: Controllable Assembly, and Dimensionality‐Dependent Catalytic Performances. Advanced Functional Materials 2021, 31 (18) https://doi.org/10.1002/adfm.202100367
  18. Vladimir V. Egorov. Dozy-Chaos Mechanics for a Broad Audience. Challenges 2020, 11 (2) , 16. https://doi.org/10.3390/challe11020016
  19. Ana M. Valencia, Michele Guerrini, Caterina Cocchi. Ab initio modelling of local interfaces in doped organic semiconductors. Physical Chemistry Chemical Physics 2020, 22 (6) , 3527-3538. https://doi.org/10.1039/C9CP06655A
  20. Mateusz Urban, Krzysztof Durka, Patrycja Górka, Gabriela Wiosna-Sałyga, Krzysztof Nawara, Piotr Jankowski, Sergiusz Luliński. The effect of locking π-conjugation in organoboron moieties in the structures of luminescent tetracoordinate boron complexes. Dalton Transactions 2019, 48 (24) , 8642-8663. https://doi.org/10.1039/C9DT01332F
  • Abstract

    Figure 1

    Figure 1. (a) Push–pull organic dye 4-(N,N-dimethyl-amino)-4-(2,3,5,6-tetra-fluorostyryl)-stilbene (C24H19F4N) and its J-aggregate viewed (b) from the ac plane and (c) from the ab plane, with the lattice vectors marked in red; crystallographic structure from CCDC no. 961738 and ref (13). (d) Brillouin zone (BZ) associated with the unit cell of the J-aggregate with the reciprocal lattice vectors indicated in blue, the high-symmetry points highlighted in red, and the path chosen for the band structure plot marked in green.

    Figure 2

    Figure 2. (a) GW energy levels (HOMO level set to zero) and frontier molecular orbitals of the isolated push–pull dye. The isovalues are fixed at 0.04 bohr–3/2. (b) Band structure of the J-aggregate computed from DFT (gray) and one-shot GW (red), where in the latter, a scissors plus stretching has been applied to the DFT energy levels. The Fermi energy is set to zero at the GW valence band maximum (VBM).

    Figure 3

    Figure 3. Isosurfaces of the squared modulus of the KS wave functions of the (a) valence band maximum and (b) conduction band minimum of the J-aggregate computed at the high-symmetry point Y. Isovalues fixed at 0.001 bohr–3.

    Figure 4

    Figure 4. Absorption spectra of (a) the push–pull dye in the gas phase and (b) in the J-aggregate. The excited states analyzed in the text (M, J, JCT) are marked by red bars with height representative of the relative oscillator strengths. The absorption in both BSE spectra is normalized with respect to the maximum value in the examined energy window. In (b), the absorption spectrum calculated from the independent quasi-particle approximation is also shown (gray-shaded area). All absorption spectra include a Lorentzian line width of 200 meV.

    Figure 5

    Figure 5. (a, b, d, e) Exciton probability density with fixed hole position (red dot), defined as |Ψλ(re, h)|2 = |⟨λ|Ψ(re)Ψ(h)|0⟩|2 = |∑cvkAvckλφck(revk*(h)|2, where Ψλ(re, h) is the exciton two-body wave function, h (re) is the hole (electron) position, Avckλ is the BSE coefficient for the excited states λ = J, JCT of the J-aggregate, and φvkck) is the occupied (unoccupied) KS electronic state with wavevector k in the BZ; views from the ab plane (a, d) and from ac plane (b, e). The exciton plot gives the probability to find the electron at position re with the hole fixed at h. (c, f) Transition density, defined as ρλ(r) = ⟨λ|Ψ(r)Ψ(r)|0⟩ = ∑cvkAvckλφck(rvk*(r), for the excited states λ = J, JCT of the J-aggregate; views from the ac plane. The transition density provides information about the charge spatial displacement associated with the specific excited state λ. Isosurfaces of the exciton wave functions (transition densities) fixed at 10% of their maximum value.

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 86 other publications.

    1. 1
      Bricks, J. L.; Slominskii, Y. L.; Panas, I. D.; Demchenko, A. P. Fluorescent J-Aggregates of Cyanine Dyes: Basic Research and Applications Review. Methods Appl. Fluoresc. 2017, 6, 012001  DOI: 10.1088/2050-6120/aa8d0d
    2. 2
      Melnikau, D.; Savateeva, D.; Susha, A. S.; Rogach, A. L.; Rakovich, Y. P. Strong Plasmon-Exciton Coupling in a Hybrid System of Gold Nanostars and J-Aggregates. Nanoscale Res. Lett. 2013, 8, 134  DOI: 10.1186/1556-276X-8-134
    3. 3
      Ferdele, S.; Jose, B.; Foster, R.; Keyes, T. E.; Rice, J. H. Strong Coupling in Porphyrin J-Aggregate Excitons and Plasmons in Nano-Void Arrays. Opt. Mater. 2017, 72, 680684,  DOI: 10.1016/j.optmat.2017.07.018
    4. 4
      Wurtz, G. A.; Evans, P. R.; Hendren, W.; Atkinson, R.; Dickson, W.; Pollard, R. J.; Zayats, A. V.; Harrison, W.; Bower, C. Molecular Plasmonics with Tunable Exciton–Plasmon Coupling Strength in J-Aggregate Hybridized Au Nanorod Assemblies. Nano Lett. 2007, 7, 12971303,  DOI: 10.1021/nl070284m
    5. 5
      Fofang, N. T.; Park, T.-H.; Neumann, O.; Mirin, N. A.; Nordlander, P.; Halas, N. J. Plexcitonic Nanoparticles: Plasmon–Exciton Coupling in Nanoshell–J-Aggregate Complexes. Nano Lett. 2008, 8, 34813487,  DOI: 10.1021/nl8024278
    6. 6
      Egorov, V. V. Theory of the J-Band: From the Frenkel Exciton to Charge Transfer. Phys. Procedia 2009, 2, 223326,  DOI: 10.1016/j.phpro.2009.07.014
    7. 7
      Jelley, E. E. Spectral Absorption and Fluorescence of Dyes in the Molecular State. Nature 1936, 138, 1009,  DOI: 10.1038/1381009a0
    8. 8
      Eisfeld, A.; Briggs, J. S. The J-Band of Organic Dyes: Lineshape and Coherence Length. Chem. Phys. 2002, 281, 6170,  DOI: 10.1016/S0301-0104(02)00594-3
    9. 9
      Eisfeld, A.; Briggs, J. S. The J- and H-Bands of Organic Dye Aggregates. Chem. Phys. 2006, 324, 376384,  DOI: 10.1016/j.chemphys.2005.11.015
    10. 10
      Walczak, P. B.; Eisfeld, A.; Briggs, J. S. Exchange Narrowing of the J Band of Molecular Dye Aggregates. J. Chem. Phys. 2008, 128, 044505  DOI: 10.1063/1.2823730
    11. 11
      Kasha, M. Energy Transfer Mechanisms and the Molecular Exciton Model for Molecular Aggregates. Radiat. Res. 1963, 20, 5570,  DOI: 10.2307/3571331
    12. 12
      Kasha, M.; Rawls, H. R.; Ashraf El-Bayoumi, M. The Exciton Model in Molecular Spectroscopy. Pure Appl. Chem. 1965, 11, 371392,  DOI: 10.1351/pac196511030371
    13. 13
      Botta, C.; Cariati, E.; Cavallo, G.; Dichiarante, V.; Forni, A.; Metrangolo, P.; Pilati, T.; Resnati, G.; Righetto, S.; Terraneo, G. Fluorine-Induced J-Aggregation Enhances Emissive Properties of a New NLO Push-Pull Chromophore. J. Mater. Chem. C 2014, 2, 52755279,  DOI: 10.1039/c4tc00665h
    14. 14
      Guerrini, M.; Calzolari, A.; Corni, S. Solid-State Effects on the Optical Excitation of Push–Pull Molecular J-Aggregates by First-Principles Simulations. ACS Omega 2018, 3, 1048110486,  DOI: 10.1021/acsomega.8b01457
    15. 15
      Hummer, K.; Puschnig, P.; Ambrosch-Draxl, C. Lowest Optical Excitations in Molecular Crystals: Bound Excitons versus Free Electron-Hole Pairs in Anthracene. Phys. Rev. Lett. 2004, 92, 147402  DOI: 10.1103/PhysRevLett.92.147402
    16. 16
      Cocchi, C.; Breuer, T.; Witte, G.; Draxl, C. Polarized Absorbance and Davydov Splitting in Bulk and Thin-Film Pentacene Polymorphs. Phys. Chem. Chem. Phys. 2018, 20, 2972429736,  DOI: 10.1039/C8CP06384B
    17. 17
      Ruini, A.; Caldas, M. J.; Bussi, G.; Molinari, E. Solid State Effects on Exciton States and Optical Properties of PPV. Phys. Rev. Lett. 2002, 88, 206403  DOI: 10.1103/PhysRevLett.88.206403
    18. 18
      Tiago, M. L.; Northrup, J. E.; Louie, S. G. Ab Initio Calculation of the Electronic and Optical Properties of Solid Pentacene. Phys. Rev. B 2003, 67, 115212  DOI: 10.1103/PhysRevB.67.115212
    19. 19
      Cudazzo, P.; Gatti, M.; Rubio, A. Excitons in Molecular Crystals from First-Principles Many-Body Perturbation Theory: Picene versus Pentacene. Phys. Rev. B 2012, 86, 195307  DOI: 10.1103/PhysRevB.86.195307
    20. 20
      Broch, K.; Dieterle, J.; Branchi, F.; Hestand, N. J.; Olivier, Y.; Tamura, H.; Cruz, C.; Nichols, V. M.; Hinderhofer, A.; Beljonne, D. Robust Singlet Fission in Pentacene Thin Films with Tuned Charge Transfer Interactions. Nat. Commun. 2018, 9, 954  DOI: 10.1038/s41467-018-03300-1
    21. 21
      Zeng, T.; Hoffmann, R.; Ananth, N. The Low-Lying Electronic States of Pentacene and Their Roles in Singlet Fission. J. Am. Chem. Soc. 2014, 136, 57555764,  DOI: 10.1021/ja500887a
    22. 22
      Refaely-Abramson, S.; da Jornada, F. H.; Louie, S. G.; Neaton, J. B. Origins of Singlet Fission in Solid Pentacene from an Ab Initio Green’s Function Approach. Phys. Rev. Lett. 2017, 119, 267401  DOI: 10.1103/PhysRevLett.119.267401
    23. 23
      Coto, P. B.; Sharifzadeh, S.; Neaton, J. B.; Thoss, M. Low-Lying Electronic Excited States of Pentacene Oligomers: A Comparative Electronic Structure Study in the Context of Singlet Fission. J. Chem. Theory Comput. 2015, 11, 147156,  DOI: 10.1021/ct500510k
    24. 24
      Beljonne, D.; Yamagata, H.; Brédas, J. L.; Spano, F. C.; Olivier, Y. Charge-Transfer Excitations Steer the Davydov Splitting and Mediate Singlet Exciton Fission in Pentacene. Phys. Rev. Lett. 2013, 110, 226402  DOI: 10.1103/PhysRevLett.110.226402
    25. 25
      Kolata, K.; Breuer, T.; Witte, G.; Chatterjee, S. Molecular Packing Determines Singlet Exciton Fission in Organic Semiconductors. ACS Nano 2014, 8, 73777383,  DOI: 10.1021/nn502544d
    26. 26
      Berkelbach, T. C.; Hybertsen, M. S.; Reichman, D. R. Microscopic Theory of Singlet Exciton Fission. III. Crystalline Pentacene. J. Chem. Phys. 2014, 141, 074705  DOI: 10.1063/1.4892793
    27. 27
      Berkelbach, T. C.; Hybertsen, M. S.; Reichman, D. R. Microscopic Theory of Singlet Exciton Fission. II. Application to Pentacene Dimers and the Role of Superexchange. J. Chem. Phys. 2013, 138, 114103  DOI: 10.1063/1.4794427
    28. 28
      Sharifzadeh, S.; Darancet, P.; Kronik, L.; Neaton, J. B. Low-Energy Charge-Transfer Excitons in Organic Solids from First-Principles: The Case of Pentacene. J. Phys. Chem. Lett. 2013, 4, 21972201,  DOI: 10.1021/jz401069f
    29. 29
      Wilson, M. W. B.; Rao, A.; Ehrler, B.; Friend, R. H. Singlet Exciton Fission in Polycrystalline Pentacene: From Photophysics toward Devices. Acc. Chem. Res. 2013, 46, 13301338,  DOI: 10.1021/ar300345h
    30. 30
      Wilson, M. W. B.; Rao, A.; Clark, J.; Kumar, R. S. S.; Brida, D.; Cerullo, G.; Friend, R. H. Ultrafast Dynamics of Exciton Fission in Polycrystalline Pentacene. J. Am. Chem. Soc. 2011, 133, 1183011833,  DOI: 10.1021/ja201688h
    31. 31
      Zimmerman, P. M.; Bell, F.; Casanova, D.; Head-Gordon, M. Mechanism for Singlet Fission in Pentacene and Tetracene: From Single Exciton to Two Triplets. J. Am. Chem. Soc. 2011, 133, 1994419952,  DOI: 10.1021/ja208431r
    32. 32
      Zimmerman, P. M.; Zhang, Z.; Musgrave, C. B. Singlet Fission in Pentacene through Multi-Exciton Quantum States. Nat. Chem. 2010, 2, 648,  DOI: 10.1038/nchem.694
    33. 33
      Schuster, R.; Knupfer, M.; Berger, H. Exciton Band Structure of Pentacene Molecular Solids: Breakdown of the Frenkel Exciton Model. Phys. Rev. Lett. 2007, 98, 037402  DOI: 10.1103/PhysRevLett.98.037402
    34. 34
      Cudazzo, P.; Sottile, F.; Rubio, A.; Gatti, M. Exciton Dispersion in Molecular Solids. J. Phys.: Condens. Matter 2015, 27, 113204  DOI: 10.1088/0953-8984/27/11/113204
    35. 35
      Hummer, K.; Ambrosch-Draxl, C. Oligoacene Exciton Binding Energies: Their Dependence on Molecular Size. Phys. Rev. B 2005, 71, 081202  DOI: 10.1103/PhysRevB.71.081202
    36. 36
      Bussi, G.; Ruini, A.; Molinari, E.; Caldas, M. J.; Puschnig, P.; Ambrosch-Draxl, C. Interchain Interaction and Davydov Splitting in Polythiophene Crystals: An Ab Initio Approach. Appl. Phys. Lett. 2002, 80, 41184120,  DOI: 10.1063/1.1483905
    37. 37
      Rangel, T.; Berland, K.; Sharifzadeh, S.; Brown-Altvater, F.; Lee, K.; Hyldgaard, P.; Kronik, L.; Neaton, J. B. Structural and Excited-State Properties of Oligoacene Crystals from First Principles. Phys. Rev. B 2016, 93, 115206  DOI: 10.1103/PhysRevB.93.115206
    38. 38
      Sharifzadeh, S.; Biller, A.; Kronik, L.; Neaton, J. B. Quasiparticle and Optical Spectroscopy of the Organic Semiconductors Pentacene and PTCDA from First Principles. Phys. Rev. B 2012, 85, 125307  DOI: 10.1103/PhysRevB.85.125307
    39. 39
      Ambrosch-Draxl, C.; Nabok, D.; Puschnig, P.; Meisenbichler, C. The Role of Polymorphism in Organic Thin Films: Oligoacenes Investigated from First Principles. New J. Phys. 2009, 11, 125010  DOI: 10.1088/1367-2630/11/12/125010
    40. 40
      Nelson, S. F.; Lin, Y.-Y.; Gundlach, D. J.; Jackson, T. N. Temperature-Independent Transport in High-Mobility Pentacene Transistors. Appl. Phys. Lett. 1998, 72, 18541856,  DOI: 10.1063/1.121205
    41. 41
      Lee, J. Y.; Roth, S.; Park, Y. W. Anisotropic Field Effect Mobility in Single Crystal Pentacene. Appl. Phys. Lett. 2006, 88, 252106  DOI: 10.1063/1.2216400
    42. 42
      Takeya, J.; Yamagishi, M.; Tominari, Y.; Hirahara, R.; Nakazawa, Y.; Nishikawa, T.; Kawase, T.; Shimoda, T.; Ogawa, S. Very High-Mobility Organic Single-Crystal Transistors with in-Crystal Conduction Channels. Appl. Phys. Lett. 2007, 90, 102120  DOI: 10.1063/1.2711393
    43. 43
      Dimitrakopoulos, C. D.; Brown, A. R.; Pomp, A. Molecular Beam Deposited Thin Films of Pentacene for Organic Field Effect Transistor Applications. J. Appl. Phys. 1996, 80, 25012508,  DOI: 10.1063/1.363032
    44. 44
      Lin, Y.-Y.; Gundlach, D. I.; Nelson, S. F.; Jackson, T. N. Pentacene-Based Organic Thin-Film Transistors. IEEE Trans. Electron Devices 1997, 44, 13251331,  DOI: 10.1109/16.605476
    45. 45
      Jin, Y.; Rang, Z.; Nathan, M. I.; Ruden, P. P.; Newman, C. R.; Frisbie, C. D. Pentacene Organic Field-Effect Transistor on Metal Substrate with Spin-Coated Smoothing Layer. Appl. Phys. Lett. 2004, 85, 44064408,  DOI: 10.1063/1.1814802
    46. 46
      Yang, S. Y.; Shin, K.; Park, C. E. The Effect of Gate-Dielectric Surface Energy on Pentacene Morphology and Organic Field-Effect Transistor Characteristics. Adv. Funct. Mater. 2005, 15, 18061814,  DOI: 10.1002/adfm.200400486
    47. 47
      Graz, I. M.; Lacour, S. P. Flexible Pentacene Organic Thin Film Transistor Circuits Fabricated Directly onto Elastic Silicone Membranes. Appl. Phys. Lett. 2009, 95, 243305  DOI: 10.1063/1.3265737
    48. 48
      Varghese, S.; Das, S. Role of Molecular Packing in Determining Solid-State Optical Properties of π-Conjugated Materials. J. Phys. Chem. Lett. 2011, 2, 863873,  DOI: 10.1021/jz200099p
    49. 49
      Köhler, A.; Wilson, J. S.; Friend, R. H. Fluorescence and Phosphorescence in Organic Materials. Adv. Mater. 2002, 14, 701707,  DOI: 10.1002/1521-4095(20020517)14:10<701::AID-ADMA701>3.0.CO;2-4
    50. 50
      Benassi, E.; Corni, S. Exciton Transfer of Azobenzene Derivatives in Self-Assembled Monolayers. J. Phys. Chem. C 2013, 117, 2502625041,  DOI: 10.1021/jp405077w
    51. 51
      Utecht, M.; Klamroth, T.; Saalfrank, P. Optical Absorption and Excitonic Coupling in Azobenzenes Forming Self-Assembled Monolayers: A Study Based on Density Functional Theory. Phys. Chem. Chem. Phys. 2011, 13, 2160821614,  DOI: 10.1039/c1cp22793a
    52. 52
      Cocchi, C.; Moldt, T.; Gahl, C.; Weinelt, M.; Draxl, C. Optical Properties of Azobenzene-Functionalized Self-Assembled Monolayers: Intermolecular Coupling and Many-Body Interactions. J. Chem. Phys. 2016, 145, 234701  DOI: 10.1063/1.4971436
    53. 53
      Cocchi, C.; Draxl, C. Understanding the Effects of Packing and Chemical Terminations on the Optical Excitations of Azobenzene-Functionalized Self-Assembled Monolayers. J. Phys.: Condens. Matter 2017, 29, 394005  DOI: 10.1088/1361-648X/aa7ca7
    54. 54
      Cocchi, C.; Draxl, C. Bound Excitons and Many-Body Effects in x-Ray Absorption Spectra of Azobenzene-Functionalized Self-Assembled Monolayers. Phys. Rev. B 2015, 92, 205105  DOI: 10.1103/PhysRevB.92.205105
    55. 55
      Hohenberg, P.; Kohn, W. Inhomogeneous Electron Gas. Phys. Rev. 1964, 136, B864B871,  DOI: 10.1103/PhysRev.136.B864
    56. 56
      Kohn, W.; Sham, L. J. Self-Consistent Equations Including Exchange and Correlation Effects. Phys. Rev. 1965, 140, A1133A1138,  DOI: 10.1103/PhysRev.140.A1133
    57. 57
      Onida, G.; Reining, L.; Rubio, A. Electronic Excitations: Density-Functional versus Many-Body Green’s-Function Approaches. Rev. Mod. Phys. 2002, 74, 601659,  DOI: 10.1103/RevModPhys.74.601
    58. 58
      Hedin, L. New Method for Calculating the One-Particle Green’s Function with Application to the Electron-Gas-Problem. Phys. Rev. 1965, 139, A796,  DOI: 10.1103/PhysRev.139.A796
    59. 59
      Strinati, G. Application of the Green’s Functions Method to the Study of the Optical Properties of Semiconductors. La Riv. Nuovo Cimento 1988, 11, 186,  DOI: 10.1007/BF02725962
    60. 60
      Hybertsen, M. S.; Louie, S. G. Electron Correlation in Semiconductors and Insulators: Band Gaps and Quasiparticle Energies. Phys. Rev. B 1986, 34, 53905413,  DOI: 10.1103/PhysRevB.34.5390
    61. 61
      Hanke, W. Dielectric Theory of Elementary Excitations in Crystals. Adv. Phys. 1978, 27, 287341,  DOI: 10.1080/00018737800101384
    62. 62
      Giannozzi, P.; Baroni, S.; Bonini, N.; Calandra, M.; Car, R.; Cavazzoni, C.; Ceresoli, D.; Chiarotti, G. L.; Cococcioni, M.; Dabo, I. QUANTUM ESPRESSO: A Modular and Open-Source Software Project for Quantum Simulations of Materials. J. Phys.: Condens. Matter 2009, 21, 395502  DOI: 10.1088/0953-8984/21/39/395502
    63. 63
      Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996, 77, 38653868,  DOI: 10.1103/PhysRevLett.77.3865
    64. 64
      Hamann, D. R. Optimized Norm-Conserving Vanderbilt Pseudopotentials. Phys. Rev. B 2013, 88, 085117  DOI: 10.1103/PhysRevB.88.085117
    65. 65
      Marini, A.; Hogan, C.; Grüning, M.; Varsano, D. Yambo: An Ab Initio Tool for Excited State Calculations. Comput. Phys. Commun. 2009, 180, 13921403,  DOI: 10.1016/j.cpc.2009.02.003
    66. 66
      Godby, R. W.; Needs, R. J. Metal-Insulator Transition in Kohn-Sham Theory and Quasiparticle Theory. Phys. Rev. Lett. 1989, 62, 11691172,  DOI: 10.1103/PhysRevLett.62.1169
    67. 67
      Larson, P.; Dvorak, M.; Wu, Z. Role of the Plasmon-Pole Model in the GW Approximation. Phys. Rev. B 2013, 88, 125205  DOI: 10.1103/PhysRevB.88.125205
    68. 68
      Stankovski, M.; Antonius, G.; Waroquiers, D.; Miglio, A.; Dixit, H.; Sankaran, K.; Giantomassi, M.; Gonze, X.; Côté, M.; Rignanese, G.-M. G0W0 Band Gap of ZnO: Effects of Plasmon-Pole Models. Phys. Rev. B 2011, 84, 241201  DOI: 10.1103/PhysRevB.84.241201
    69. 69
      Lebègue, S.; Arnaud, B.; Alouani, M.; Bloechl, P. E. Implementation of an All-Electron GW Approximation Based on the Projector Augmented Wave Method without Plasmon Pole Approximation: Application to Si, SiC, AlAs, InAs, NaH, and KH. Phys. Rev. B 2003, 67, 155208  DOI: 10.1103/PhysRevB.67.155208
    70. 70
      Bruneval, F.; Rangel, T.; Hamed, S. M.; Shao, M.; Yang, C.; Neaton, J. B. MOLGW 1: Many-Body Perturbation Theory Software for Atoms, Molecules, and Clusters. Comput. Phys. Commun. 2016, 208, 149161,  DOI: 10.1016/j.cpc.2016.06.019
    71. 71
      Bruneval, F.; Marques, M. A. L. Benchmarking the Starting Points of the GW Approximation for Molecules. J. Chem. Theory Comput. 2013, 9, 324329,  DOI: 10.1021/ct300835h
    72. 72
      Bruneval, F.; Rangel, T.; Hamed, S. M.; Shao, M.; Yang, C.; Neaton, J. B. MOLGW 1: Many-Body Perturbation Theory Software for Atoms, Molecules, and Clusters. Comput. Phys. Commun. 2016, 208, 149161,  DOI: 10.1016/j.cpc.2016.06.019
    73. 73
      van der Horst, J.; Bobbert, P.; de Jong, P.; Michels, M.; Brocks, G.; Kelly, P. Ab Initio Prediction of the Electronic and Optical Excitations in Polythiophene: Isolated Chains versus Bulk Polymer. Phys. Rev. B 2000, 61, 1581715826,  DOI: 10.1103/PhysRevB.61.15817
    74. 74
      Cocchi, C.; Draxl, C. Optical Spectra from Molecules to Crystals: Insight from Many-Body Perturbation Theory. Phys. Rev. B 2015, 92, 5126,  DOI: 10.1103/PhysRevB.92.205126
    75. 75
      Alvarado, S. F.; Seidler, P. F.; Lidzey, D. G.; Bradley, D. D. C. Direct Determination of the Exciton Binding Energy of Conjugated Polymers Using a Scanning Tunneling Microscope. Phys. Rev. Lett. 1998, 81, 10821085,  DOI: 10.1103/PhysRevLett.81.1082
    76. 76
      Campbell, I. H.; Hagler, T. W.; Smith, D. L.; Ferraris, J. P. Direct Measurement of Conjugated Polymer Electronic Excitation Energies Using Metal/Polymer/Metal Structures. Phys. Rev. Lett. 1996, 76, 19001903,  DOI: 10.1103/PhysRevLett.76.1900
    77. 77
      Barth, S.; Bässler, H. Intrinsic Photoconduction in PPV-Type Conjugated Polymers. Phys. Rev. Lett. 1997, 79, 44454448,  DOI: 10.1103/PhysRevLett.79.4445
    78. 78
      Varsano, D.; Marini, A.; Rubio, A. Optical Saturation Driven by Exciton Confinement in Molecular Chains: A Time-Dependent Density-Functional Theory Approach. Phys. Rev. Lett. 2008, 101, 133002  DOI: 10.1103/PhysRevLett.101.133002
    79. 79
      Cocchi, C.; Prezzi, D.; Ruini, A.; Caldas, M. J.; Molinari, E. Optical Properties and Charge-Transfer Excitations in Edge-Functionalized All-Graphene Nanojunctions. J. Phys. Chem. Lett. 2011, 2, 13151319,  DOI: 10.1021/jz200472a
    80. 80
      Ruini, A. Ab Initio Optical Absorption in Conjugated Polymers: The Role of Dimensionality. Phys. Scr. 2004, T109, 121,  DOI: 10.1238/Physica.Topical.109a00121
    81. 81
      Barford, W. Electronic and Optical Properties of Conjugated Polymers; International Series of Monographs on Physics; OUP: Oxford, 2005.
    82. 82
      Dreuw, A.; Head-Gordon, M. Single-Reference Ab Initio Methods for the Calculation of Excited States of Large Molecules. Chem. Rev. 2005, 105, 40094037,  DOI: 10.1021/cr0505627
    83. 83
      Dreuw, A.; Weisman, J. L.; Head-gordon, M. Long-Range Charge-Transfer Excited States in Time-Dependent Density Functional Theory Require non-local Exchange. J. Chem. Phys. 2003, 119, 2943,  DOI: 10.1063/1.1590951
    84. 84
      Dreuw, A.; Head-Gordon, M. Failure of Time-Dependent Density Functional Theory for Long-Range Charge-Transfer Excited States: The Zincbacteriochlorin–Bacteriochlorin and Bacteriochlorophyll–Spheroidene Complexes. J. Am. Chem. Soc. 2004, 126, 40074016,  DOI: 10.1021/ja039556n
    85. 85
      Hummer, K.; Puschnig, P.; Ambrosch-Draxl, C. Ab Initio Study of Anthracene under High Pressure. Phys. Rev. B 2003, 67, 184105  DOI: 10.1103/PhysRevB.67.184105
    86. 86
      Puschnig, P.; Hummer, K.; Ambrosch-Draxl, C.; Heimel, G.; Oehzelt, M.; Resel, R. Electronic, Optical, and Structural Properties of Oligophenylene Molecular Crystals under High Pressure: An Ab Initio Investigation. Phys. Rev. B 2003, 67, 235321  DOI: 10.1103/PhysRevB.67.235321
  • Supporting Information

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b11709.

    • Electronic and optical properties of the isolated push–pull monomer and the J-aggregate (PDF)


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.