Vibrationally high-resolved electronic spectra of MCl2 (M=C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl2(.).
We systematically studied the vibrational-resolved electronic spectra of group IV dichlorides using the Franck-Condon approximation combined with the Duschinsky and Herzberg-Teller effects in harmonic and anharmonic frameworks (only the simulation of absorption spectra includes the anharmonicity). Calculated results showed that the band shapes of simulated spectra are in accordance with those of the corresponding experimental or theoretical ones. We found that the symmetric bend mode in progression of absorption is the most active one, whereas the main contributor in photoelectron spectra is the symmetric stretching mode. Moreover, the Duschinsky and anharmonic effects exert weak influence on the absorption spectra, except for PbCl2 molecule. The theoretical insights presented in this work are significant in understanding the photophysical properties of MCl2 (M=C, Si, Ge, Sn, Pb) and studying the Herzberg-Teller and the anharmonic effects on the absorption spectra of new dichlorides of this main group.
Key Laboratory of Luminescence and Real-Time Analytical chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Yibin
Y
Ran
Key Laboratory of Luminescence and Real-Time Analytical chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Min
M
Pang
Key Laboratory of Luminescence and Real-Time Analytical chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Wei
W
Shen
Key Laboratory of Luminescence and Real-Time Analytical chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Ming
M
Li
Key Laboratory of Luminescence and Real-Time Analytical chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China. Electronic address: herx@swu.edu.cn.
Rongxing
R
He
Absorption and emission spectra; Anharmonic; Franck–Condon; Herzberg–Teller; Photoelectron spectra