Anharmonic Franck-Condon simulation of the absorption and fluorescence spectra for the low-lying S 1 and S 2 excited states of pyrimidine

Ling Yang, Chaoyuan Zhu*, Jianguo Yu, Sheng Hsien Lin

*此作品的通信作者

研究成果: Article同行評審

15 引文 斯高帕斯(Scopus)

摘要

Intensities and profiles of vibronic spectra of the low-lying singlet excited states were investigated with anharmonic and harmonic Franck-Condon simulations for pyrimidine. The first-order anharmonic correction shows dynamic shift of spectra that is exactly same as difference of reorganization energy between ground and excited states. The first-order correction show intensity enhancement of absorption and intensity weakening of fluorescence for S 1 state, and dynamic shift is also significant. On the other hand, the first-order correction is negligible for S 2 state. The main spectral progressions are well described by totally symmetry modes ν 6a, ν 1 and ν 12. One mode from non-total symmetry ν 16a contributes to the weak band at 16a 2 transition for S 1 state. Four ab initio methods were employed in simulation; CASSCF, CASPT2, DFT and TD-DFT, and coupled-cluster singles-doubles (CCSD) and the equation-of-motion (EOM-CCSD) methods. They all work well, but CASSCF method show the best agreement with experiment for the weak-band intensities.

原文English
頁(從 - 到)126-136
頁數11
期刊Chemical Physics
400
DOIs
出版狀態Published - 25 5月 2012

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