Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

Garza, Alejandro J.; Wazzan, Nuha; Asiri, Abdullah M.; Scuseria, Gustavo E.

doi:10.1021/jp510062b

Cited by 55 publications

(43 citation statements)

References 93 publications

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“…15 In particular, longrange corrected (LC) hybrids, which have large fractions of HF exchange in the LR, dramatically improve upon (semi)local functionals in the description of problems where self-interaction is pathological. [16][17][18][19][20][21][22][23][24][25][26][27][28][29] Such a practical solution is not known for the problem of static correlation. Often, the most common path for dealing with static correlation is to abandon density functionals and work with multireference (MR) wavefunction methods, despite the latter being inefficient for capturing dynamic correlation.…”

Section: Introductionmentioning

confidence: 99%

Range separated hybrids of pair coupled cluster doubles and density functionals

Garza

Bulik

Henderson

et al. 2015

Phys. Chem. Chem. Phys.

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Pair coupled cluster doubles (pCCD) is a size-consistent, size-extensive, low-cost simplification of CCD that has been shown to be able to describe static correlation without breaking symmetry. We combine pCCD with Kohn-Sham functionals of the density and the local pair density in order to incorporate dynamic correlation in pCCD while maintaining its low cost. Double counting is eliminated by splitting the (interelectron) Coulomb operator into complementary short- and long-range parts, and evaluating the two-body energy with pCCD in the long-range and with density functionals in the short-range. This simultaneously suppresses self-interaction in the Hartree-exchange term of the functionals. Generalizations including a fraction of wavefunction two-body energy in the short-range are also derived and studied. The improvement of our pCCD+DFT hybrids over pCCD is demonstrated in calculations on benchmarks where both types of correlation are important.

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Section: Introductionmentioning

confidence: 99%

Range separated hybrids of pair coupled cluster doubles and density functionals

Garza

Bulik

Henderson

et al. 2015

Phys. Chem. Chem. Phys.

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“…For small molecules, ω tuning has been reported to improve prediction of ionization potentials, 29,34,35,38,45 polarizabilities, 48 hyperpolarizabilities, 43,44 and fundamental gaps, 34,39,40,42,46 relative to LRC functionals with default ω values. Furthermore, FIG.…”

Section: Introductionmentioning

confidence: 99%

Density-functional errors in ionization potential with increasing system size

Whittleton

Vazquez

Isborn

et al. 2015

The Journal of Chemical Physics

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This work investigates the effects of molecular size on the accuracy of density-functional ionization potentials for a set of 28 hydrocarbons, including series of alkanes, alkenes, and oligoacenes. As the system size increases, delocalization error introduces a systematic underestimation of the ionization potential, which is rationalized by considering the fractional-charge behavior of the electronic energies. The computation of the ionization potential with many density-functional approximations is not size-extensive due to excessive delocalization of the incipient positive charge. While inclusion of exact exchange reduces the observed errors, system-specific tuning of long-range corrected functionals does not generally improve accuracy. These results emphasize that good performance of a functional for small molecules is not necessarily transferable to larger systems.

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“…Recently, the success of OT-RSH to achieve proper HOMO−LUMO gaps was indicated to stem from the inclusion of the exact exchange by analyzing hyperpolarizabilities of several large CT molecular systems. 53 In the OT-RSH scheme, the Coulomb interaction takes the generalized form: …”

Section: ■ Introductionmentioning

confidence: 99%

Calculating High Energy Charge Transfer States Using Optimally Tuned Range-Separated Hybrid Functionals

Manna

Lee

McMahon

et al. 2015

J. Chem. Theory Comput.

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Recently developed optimally tuned range-separated hybrid (OT-RHS) functionals within time-dependent density functional theory have been shown to address existing limitations in calculating charge transfer excited state energies. The RSH success in improving the calculation of CT states stems from enforcing the correspondence of the frontier molecular orbitals (FMOs) to physical properties, where the highest occupied MO energy relates to the ionization potential and the lowest unoccupied MO energy relates to the electron affinity. However, in this work, we show that a less accurate description of CT states that involves non-FMOs is afforded by the RSH approach. In order to achieve a high quality description of such higher energy CT states, the parameter tuning procedure, which lies at the foundation of the RSH approach, needs to be generalized to consider the CT process. We demonstrate the need for improved description of such CT states in donor-acceptor systems, where the optimal tuning parameter is accounting for the state itself.

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Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

Cited by 55 publications

References 93 publications

Range separated hybrids of pair coupled cluster doubles and density functionals

Range separated hybrids of pair coupled cluster doubles and density functionals

Density-functional errors in ionization potential with increasing system size

Calculating High Energy Charge Transfer States Using Optimally Tuned Range-Separated Hybrid Functionals

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