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Title: Time-dependent density functional theory assessment of UV absorption of benzoic acid derivatives

Abstract

Benzoic acid (BA) derivatives of environmental relevance exhibit various photophysical and photochemical characteristics. Here, time-dependent density functional theory (TDDFT) is used to calculate photoexcitations of eight selected BAs and the results are compared with UV spectra determined experimentally. High-level gas-phase EOM-CCSD calculations and experimental aqueous-phase spectra were used as the references for the gas-phase and aqueous-phase TDDFT results, respectively. A cluster-continuum model was used in the aqueous-phase calculations. Among the 15 exchange correlation (XC) functionals assessed, five functionals, including the meta-GGA hybrid M06-2X, double hybrid B2PLYPD, and range-separated functionals CAM-B3LYP, ωB97XD, and LC- ωPBE, were found to be in excellent agreement with the EOM-CCSD gas-phase calculations. These functionals furnished excitation energies consistent with the pH dependence of the experimental spectra with a standard deviation (STDEV) of 0.20 eV. A molecular orbital analysis revealed a πσ* feature of the low-lying transitions of the BAs. Furthermore, the CAM-B3LYP functional showed the best overall performance and therefore shows promise for TDDFT calculations of processes involving photoexcitations of benzoic acid derivatives.

Authors:
 [1];  [2];  [2];  [2];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1265968
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 116; Journal Issue: 48; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Guo, Hao -Bo, He, Feng, Gu, Baohua, Liang, Liyuan, and Smith, Jeremy C. Time-dependent density functional theory assessment of UV absorption of benzoic acid derivatives. United States: N. p., 2012. Web. doi:10.1021/jp3084293.
Guo, Hao -Bo, He, Feng, Gu, Baohua, Liang, Liyuan, & Smith, Jeremy C. Time-dependent density functional theory assessment of UV absorption of benzoic acid derivatives. United States. doi:10.1021/jp3084293.
Guo, Hao -Bo, He, Feng, Gu, Baohua, Liang, Liyuan, and Smith, Jeremy C. Wed . "Time-dependent density functional theory assessment of UV absorption of benzoic acid derivatives". United States. doi:10.1021/jp3084293.
@article{osti_1265968,
title = {Time-dependent density functional theory assessment of UV absorption of benzoic acid derivatives},
author = {Guo, Hao -Bo and He, Feng and Gu, Baohua and Liang, Liyuan and Smith, Jeremy C.},
abstractNote = {Benzoic acid (BA) derivatives of environmental relevance exhibit various photophysical and photochemical characteristics. Here, time-dependent density functional theory (TDDFT) is used to calculate photoexcitations of eight selected BAs and the results are compared with UV spectra determined experimentally. High-level gas-phase EOM-CCSD calculations and experimental aqueous-phase spectra were used as the references for the gas-phase and aqueous-phase TDDFT results, respectively. A cluster-continuum model was used in the aqueous-phase calculations. Among the 15 exchange correlation (XC) functionals assessed, five functionals, including the meta-GGA hybrid M06-2X, double hybrid B2PLYPD, and range-separated functionals CAM-B3LYP, ωB97XD, and LC- ωPBE, were found to be in excellent agreement with the EOM-CCSD gas-phase calculations. These functionals furnished excitation energies consistent with the pH dependence of the experimental spectra with a standard deviation (STDEV) of 0.20 eV. A molecular orbital analysis revealed a πσ* feature of the low-lying transitions of the BAs. Furthermore, the CAM-B3LYP functional showed the best overall performance and therefore shows promise for TDDFT calculations of processes involving photoexcitations of benzoic acid derivatives.},
doi = {10.1021/jp3084293},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 48,
volume = 116,
place = {United States},
year = {2012},
month = {11}
}