Performance of TDDFT Vertical Excitation Energies of Core‐Substituted Naphthalene Diimides. Issue 15 (6th March 2020)

• Record Type: Journal Article
• Authors: Narsaria, Ayush K.; Ruijter, Julian D.; Hamlin, Trevor A.; Ehlers, Andreas W.; Guerra, Célia Fonseca; Lammertsma, Koop; Bickelhaupt, F. Matthias
• Is Part Of: Journal of computational chemistry. Volume 41:Issue 15(2020)
• Page Start: 1448
• Page End: 1455
• Publication Date: 2020-03-06
• Subjects: charge‐transfer excitations -- density functional calculations -- naphthalene diimides -- solvent effects -- time‐dependent density functional theory; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.26188
• Languages: English
• ISSNs: 0192-8651

Abstract

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. Abstract : We have evaluated the performance of various exchange‐correlation functionals for reproducing the experimental absorption maximum in core‐substituted naphthalene diimides through quantum‐chemical TDDFT and statistical calculations. Results are analyzed and an appropriate TDDFT protocol has been developed.