Performance of TDDFT Vertical Excitation Energies of Core-Substituted Naphthalene Diimides.
J Comput Chem
; 41(15): 1448-1455, 2020 06 05.
Article
en En
| MEDLINE
| ID: mdl-32142173
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 (λmax ) 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 λmax . We highlight the importance of including solvent effects for optimal agreement with the λmax . 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 λmax 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.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
J Comput Chem
Asunto de la revista:
QUIMICA
Año:
2020
Tipo del documento:
Article
País de afiliación:
Países Bajos