Title: Singlet-triplet energy gap of multiresonant molecular systems: A double hybrid time-dependent density functional theory study
Abstract: Singlet–triplet energy gaps (ΔEST) for multiresonant molecular systems are investigated within time-dependent density functional theory (TDDFT), using conventional linear response TDDFT (LR-TDDFT) and double hybrid TDDFT (DH-TDDFT) schemes. LR-TDDFT methods systematically overestimate ΔEST; on the other hand, by explicitly taking double excitation characters into consideration, DH-TDDFT considerably improves the gap problem. Further theoretical analysis shows that DH-TDDFT calculations also work for the description of negative gap situations, which LR-TDDFT intrinsically fails. The present findings demonstrate the applicability of TDDFT-based methods for predicting ΔEST as a relatively low-cost computational approach, encouraging us to develop new exchange-correlation functionals suited for DH-TDDFT calculations.
Publication Year: 2022
Publication Date: 2022-10-01
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 9
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