TY - JOUR
T1 - Theoretical study of the absorption and emission spectrum and non-adiabatic excited state dynamics of gas-phase xanthone
AU - Chin, Chih Hao
AU - Zhu, Tong
AU - Zhang, John Zeng Hui
N1 - Funding Information:
This work was supported by the National Natural Science Foundation of China (Grants Nos. 91,641,116, 21,433,004, 91,753,103 and 21,933,010), and the NYU Global Seed Grant, and the Laboratory and Equipment Management Office of ECNU. We also thank the ECNU Multifunctional Platform for Innovation (No. 001) for providing us computer time. CHC, who was Prof. S. H. Lin's postdoctoral assistant in IAMS during 2004–2008, thanks his active leadership in researching the principles of molecular spectroscopy, photochemistry, and the chemical reaction dynamics for complex reaction mechanism.
Funding Information:
National Natural Science Foundation of China, Grant/Award Numbers: 91641116, 21433004, 91753103, 21933010 Funding information
Publisher Copyright:
© 2023 Chemical Society Located in Taipei and Wiley-VCH GmbH.
PY - 2023/3
Y1 - 2023/3
N2 - The ground, singlet, and triplet excited state structures (S1, S2, T1, and T2) of xanthone have been calculated and characterized in the adiabatic representation by using time-dependent density functional theory (TDDFT). However, the fast intramolecular transition mechanisms of xanthone are still under debate, and so we perform non-adiabatic excited state dynamics of the photochemistry of xanthone gas phase and find that it follows El-Sayed's rule. Electronic transition mechanism of xanthone is sequential from the S2 state: the singlet internal conversion (IC) time from S2 (1ππ*) to S1 (1nπ*) is 3.85 ps, the intersystem crossing (ISC) from S1 (1nπ*) to T2 (3ππ*) takes 4.76 ps, and the triplet internal conversion from T2 (3ππ*) to T1 (3nπ*) takes 472 fs. The displaced oscillator, Franck–Condon approximation, and one-photon excitation equations were used to simulate the absorption spectra of S0 → S2 transition, with v55 being most crucial for S0 structure; the fluorescence spectra of S1 → S0 transition with v47 for S1; and the phosphorescence spectra of T1 → S0 transition with v4 for T1. Our method can reproduce the experimental absorption, fluorescence, and phosphorescence spectra of gas-phase xanthone.
AB - The ground, singlet, and triplet excited state structures (S1, S2, T1, and T2) of xanthone have been calculated and characterized in the adiabatic representation by using time-dependent density functional theory (TDDFT). However, the fast intramolecular transition mechanisms of xanthone are still under debate, and so we perform non-adiabatic excited state dynamics of the photochemistry of xanthone gas phase and find that it follows El-Sayed's rule. Electronic transition mechanism of xanthone is sequential from the S2 state: the singlet internal conversion (IC) time from S2 (1ππ*) to S1 (1nπ*) is 3.85 ps, the intersystem crossing (ISC) from S1 (1nπ*) to T2 (3ππ*) takes 4.76 ps, and the triplet internal conversion from T2 (3ππ*) to T1 (3nπ*) takes 472 fs. The displaced oscillator, Franck–Condon approximation, and one-photon excitation equations were used to simulate the absorption spectra of S0 → S2 transition, with v55 being most crucial for S0 structure; the fluorescence spectra of S1 → S0 transition with v47 for S1; and the phosphorescence spectra of T1 → S0 transition with v4 for T1. Our method can reproduce the experimental absorption, fluorescence, and phosphorescence spectra of gas-phase xanthone.
KW - Franck–Condon factors
KW - Huang–Rhys factors
KW - non-adiabatic processes
KW - radiationless transition
KW - vibronic theory
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U2 - 10.1002/jccs.202200422
DO - 10.1002/jccs.202200422
M3 - Article
AN - SCOPUS:85145412738
SN - 0009-4536
VL - 70
SP - 372
EP - 385
JO - Journal of the Chinese Chemical Society
JF - Journal of the Chinese Chemical Society
IS - 3
ER -