Screened Range-Separated Hybrid Functional with Polarizable Continuum Model Overcomes Challenges in Describing Triplet Excitations in the Condensed Phase Using TDDFT

Begam, Khadiza; Bhandari, Srijana; Maiti, Buddhadev; Dunietz, Barry D.

doi:10.1021/acs.jctc.0c00086

Screened Range-Separated Hybrid Functional with Polarizable Continuum Model Overcomes Challenges in Describing Triplet Excitations in the Condensed Phase Using TDDFT

Journal Article · Mon Apr 20 00:00:00 EDT 2020 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.0c00086· OSTI ID:1803003

Begam, Khadiza ^[1]; Bhandari, Srijana ^[2]; Maiti, Buddhadev ^[2]; ^[2]

Kent State Univ., Kent, OH (United States); Kent State University
Kent State Univ., Kent, OH (United States)

Long range-corrected (LRC) or range-separated hybrid (RSH) functionals where the long-range (LR) limit of electronic interactions is set to the exact exchange have been shown to correct the tendency of traditional density functional theory (DFT) to underestimate the frontier orbital gap. Consequently, the use of such functionals in calculating electronic excited states using linear response based time-dependent DFT (TDDFT) has been successful in correcting the tendency for underestimating the energies of charge transfer states by DFT-based calculations. More recently formulations of functionals that attenuate the LR limit to address condensed-phase effects to polarize the electronic density have been reported. In particular screened RSH (SRSH) combined with polarizable continuum model (PCM) was benchmarked successfully in reproducing the fundamental gap and charge transfer state energies of molecular systems in the condensed phase. Here we use SRSH-PCM to address triplet excited states, and show its success in obtaining correspondence of the low-lying triplet states to the singlet–triplet gap in a similar way that the fundamental orbital gap corresponds to electron removal and addition energies. Importantly, the accuracy of the SRSH-PCM in calculating triplet excitations stands on the polarization consistent framework in addressing the scalar dielectric constant and without affecting the optimal tuning by triplet energies. Finally, the prospect of even further improving the SRSH-PCM accuracy in calculating triplet states can be achieved by optimal tuning on the basis of the spin multiplicity gap.

View Accepted Manuscript (DOE)

Research Organization:: Kent State Univ., Kent, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016501

OSTI ID:: 1803003

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 5 Vol. 16; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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