Femtosecond Wavepacket Dynamics Reveals the Molecular Structures in the Excited (S1) and Cationic (D0) States

被引:4
|
作者
Kim, Junggil [1 ]
Woo, Kyung Chul [1 ,2 ]
Kim, Sang Kyu [1 ]
机构
[1] Korea Adv Inst Sci & Technol, Dept Chem, Daejeon 34141, South Korea
[2] Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, Singapore 637371, Singapore
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2021年 / 125卷 / 30期
基金
新加坡国家研究基金会;
关键词
TEMPERATURE PHOTOELECTRON-SPECTROSCOPY; NONADIABATIC BIFURCATION DYNAMICS; CONICAL INTERSECTION SEAM; CONFORMATIONAL PREFERENCES; PHOTODISSOCIATION DYNAMICS; ROTATIONAL-ISOMERISM; AB-INITIO; THIOANISOLE; ANISOLE; SPECTRA;
D O I
10.1021/acs.jpca.1c04976
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Molecular structures in the electronically excited (S-1) and cationic (D-0) states of 2-fluorothioanisole (2-FTA) have been precisely refined from the real-time dynamics of the femtosecond (fs) wavepacket prepared by the coherent excitation of the Franck-Condon active out-of-plane torsional modes in the S-1 <- S-0 transition at 285 nm. The simulation to reproduce the experiment in terms of the beating frequencies gives the nonplanar geometry of 2-FTA in S-1, where the out-of-plane dihedral angle (phi) of the S-CH3 moiety is 51 degrees with respect to the molecular plane. The behavior of the fs wavepacket in terms of the amplitudes and phases with the change of the probe (ionization) wavelength (lambda(probe) = 300-330 nm) provides the otherwise veiled structure of the cationic D-0 state. While the 2-FTA cation adopts the planar geometry (phi = 0 degrees) at the global minimum, it is found to have a vertical minimum at phi approximate to 135 degrees from the perspective of the D-0 <- S-1 vertical transition. Ab initio calculations support the experiment quite well although the simulation using the model potentials could improve the match with the experiment, giving the new interpretation for the previously disputed photoelectron spectroscopic results.
引用
收藏
页码:6629 / 6635
页数:7
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