期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 116, 期 48, 页码 11870-11879出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp3084293
关键词
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资金
- Office of Biological and Environmental Research of the U.S. Department of Energy (DOE)
- US DOE [DE-AC05-00OR22725]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
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, omega B97XD, and LC-omega PBE, 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 similar to 0.20 eV. A molecular orbital analysis revealed a pi sigma* feature of the low-lying transitions of the BAs. The CAM-B3LYP functional showed the best overall performance and therefore shows promise for TDDFT calculations of processes involving photoexcitations of benzoic acid derivatives.
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