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

Ayush K. Narsaria; Julian D. Ruijter; Trevor A. Hamlin; Andreas W. Ehlers; Célia Fonseca Guerra; Koop Lammertsma; F. Matthias Bickelhaupt

doi:10.1002/jcc.26188

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

Ayush K. Narsaria, Julian D. Ruijter, Trevor A. Hamlin, Andreas W. Ehlers, Célia Fonseca Guerra, Koop Lammertsma, F. Matthias Bickelhaupt

Chemical Sciences

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

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 (λ_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 λ_max. We highlight the importance of including solvent effects for optimal agreement with the λ_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 λ_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.

Original language	English
Pages (from-to)	1448-1455
Number of pages	8
Journal	Journal of Computational Chemistry
Volume	41
Issue number	15
DOIs	https://doi.org/10.1002/jcc.26188
Publication status	Published - 5 Jun 2020

Keywords

charge-transfer excitations
density functional calculations
naphthalene diimides
solvent effects
time-dependent density functional theory

ASJC Scopus subject areas

General Chemistry
Computational Mathematics

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10.1002/jcc.26188

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title = "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 (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.",

keywords = "charge-transfer excitations, density functional calculations, naphthalene diimides, solvent effects, time-dependent density functional theory",

author = "Narsaria, {Ayush K.} and Ruijter, {Julian D.} and Hamlin, {Trevor A.} and Ehlers, {Andreas W.} and Guerra, {C{\'e}lia Fonseca} and Koop Lammertsma and Bickelhaupt, {F. Matthias}",

note = "Publisher Copyright: {\textcopyright} 2020 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.",

year = "2020",

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AU - Narsaria, Ayush K.

AU - Ruijter, Julian D.

AU - Hamlin, Trevor A.

AU - Ehlers, Andreas W.

AU - Guerra, Célia Fonseca

AU - Lammertsma, Koop

AU - Bickelhaupt, F. Matthias

PY - 2020/6/5

Y1 - 2020/6/5

N2 - 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.

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

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Keywords

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