Performance of TDDFT Vertical Excitation Energies of Core-Substituted Naphthalene Diimides.

ABSTRACT: We have evaluated the performance of various density functionals, covering generalized gradient approximation (GGA), global hybrid (GH) and range-separated hybrid (RSH), using time dependent density functional theory (TDDFT) for computing vertical excitation energies against experimental absorption maximum (?_max ) for a set of 10 different core-substituted naphthalene diimides (cNDI) recorded in dichloromethane. The computed excitation in case of GH PBE0 is most accurate while the trend is most systematic with RSH LCY-BLYP compared to ?_max . We highlight the importance of including solvent effects for optimal agreement with the ?_max . Increasing the basis set size from TZ2P to QZ4P has a negligible influence on the computed excitation energies. Notably, RSH CAMY-B3LYP gave the least error for charge-transfer excitation. The poorest agreement with ?_max is obtained with semi-local GGA functionals. Use of the optimally-tuned RSH LCY-BLYP* is not recommended because of the high computational cost and marginal improvement in results.

SUBMITTER: Narsaria AK 

PROVIDER: S-EPMC7317478 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature