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 - 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 -