Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case

Sini, Gjergji; Sears, John S.; Brédas, Jean‐Luc

doi:10.1021/ct1005517

Cited by 153 publications

(155 citation statements)

References 63 publications

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“…It has been suggested recently that an improved description of chargetransfer states can be obtained by employing range-separated hybrid functionals, especially those with system-tuned rangeseparation parameters [38]. While there are now multiple examples of applying these functionals to the donor-acceptor complexes [39,40], their application to donor-acceptor crystals is still missing. Such investigations in our group are now underway, and the related results will be reported elsewhere.…”

Section: Resultsmentioning

confidence: 99%

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

et al. 2014

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We evaluate the impact that the amount of nonlocal Hartree-Fock (%HF) exchange included in a hybrid density functional has on the microscopic parameters (transfer integrals, band gaps, bandwidths, and effective masses) describing charge transport in high-mobility organic crystals. We consider both crystals based on a single molecule, such as pentacene, and crystals based on mixed-stack charge-transfer systems, such as dibenzo-TTF-TCNQ. In the pentacene crystal, the band gap decreases and the effective masses increase linearly with an increase in the amount of %HF exchange. In contrast, in the charge-transfer crystals, while the band gap increases linearly, the effective masses vary only slightly with an increase in %HF exchange. We show that the superexchange nature of the electronic couplings in charge-transfer systems is responsible for this peculiar evolution of the effective masses. We compare the density functional theory results with results obtained within the G 0 W 0 approximation as a way of benchmarking the optimal amount of %HF exchange needed in a given functional.

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Section: Resultsmentioning

confidence: 99%

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

et al. 2014

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“…A description of donor-acceptor complexes from first principles is desirable to achieve an atomistic understanding of charge-transfer processes and their impact on electronic properties. However, charge transfer remains a major challenge for presently available first-principles techniques [3,4].…”

Section: Introductionmentioning

confidence: 99%

First-principles description of charge transfer in donor-acceptor compounds from self-consistent many-body perturbation theory

et al. 2014

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We investigate charge transfer in prototypical molecular donor-acceptor compounds using hybrid density functional theory (DFT) and the GW approximation at the perturbative level (G 0 W 0 ) and at full self-consistency (sc-GW ). For the systems considered here, no charge transfer should be expected at large intermolecular separation according to photoemission experiments and accurate quantum-chemistry calculations. The capability of hybrid exchange-correlation functionals of reproducing this feature depends critically on the fraction of exact exchange α, as for small values of α spurious fractional charge transfer is observed between the donor and the acceptor. G 0 W 0 based on hybrid DFT yields the correct alignment of the frontier orbitals for all values of α. However, G 0 W 0 has no capacity to alter the ground-state properties of the system because of its perturbative nature. The electron density in donor-acceptor compounds thus remains incorrect for small α values. In sc-GW , where the Green's function is obtained from the iterative solution of the Dyson equation, the electron density is updated and reflects the correct description of the level alignment at the GW level, demonstrating the importance of self-consistent many-body approaches for the description of ground-and excited-state properties in donor-acceptor systems.

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“…The results of DFT methods are compared to those of HF, MP2 and CCSD(T) ab initio calculations. Through this comparison, we aimed to assess the ability of commonly used exchange-correlation functionals to describe cooperative EDA interactions (note that some previous DFT studies have already been devoted to EDA systems [26,27]). Then, using the symmetry-adapted perturbation theory (SAPT), [28,29] we have evaluated the electrostatic, induction, exchange and dispersion contributions to the interaction energy in order to clarify their respective role in the stabilization of conventional and unconventional complexes of carbonyl dioxide with carbonyl compounds.…”

Section: Introductionmentioning

confidence: 99%

Theoretical insights on electron donor–acceptor interactions involving carbon dioxide

San‐Fabián

Ingrosso

Lambert

et al. 2014

Chemical Physics Letters

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Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case

Cited by 153 publications

References 63 publications

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

First-principles description of charge transfer in donor-acceptor compounds from self-consistent many-body perturbation theory

Theoretical insights on electron donor–acceptor interactions involving carbon dioxide

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