Premium
Solvent effect on the initial structural dynamics of benzaldehyde in the S 3 (ππ*) state—Resonance Raman spectroscopic study
Author(s) -
Chen Jia,
Jiang Xuelian,
Xue Jiadan,
Wang Huigang,
Zheng Xuming
Publication year - 2019
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.5573
Subject(s) - chemistry , cyclohexane , raman spectroscopy , resonance raman spectroscopy , resonance (particle physics) , absorption band , excited state , photochemistry , absorption spectroscopy , analytical chemistry (journal) , atomic physics , organic chemistry , optics , physics
The excited‐state structural dynamics of benzaldehyde (BA) after population to the S 3 (π H‐1 π L *) light‐absorbing state were studied using resonance Raman spectroscopy and complete active space self‐consistent field (CASSCF) calculations. The C‐band absorption cross section and the corresponding absolute resonance Raman cross sections in cyclohexane and methanol were simulated using the time‐dependent wave‐packets formalism, respectively. The results indicate that the major structural dynamics of BA and the homogeneous broadening of the absorption spectrum in cyclohexane are similar to those of BA in methanol or acetophenone (AP) in cyclohexane, whereas the inhomogeneous broadening of BA in cyclohexane is significantly different from that in methanol. It is proposed that the initial decay pathway of BA upon the C‐band absorption is mostly towards S 3 S 2 and partly to S 3,min . The roles of hydrogen bonding and polar–polar interaction in the spectral broadenings are discussed.