对间氯苯甲硫醚和3-氯硫代苯甲醚分子结构的光电离光谱及理论研究。

Zhang Zhe, Du Yikui, Hou Gao-Lei, Gao Hong

Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

University of Chinese Academy of Sciences, Beijing 100049, China.

ACS Omega. 2022 Mar 7;7(10):8456-8465. doi: 10.1021/acsomega.1c06003. eCollection 2022 Mar 15.

Resonance-enhanced two-photon ionization (R2PI) and mass-analyzed threshold ionization (MATI) spectra are measured for the and 3-chlorothioanisole (3ClTA). The first electronic excitation energy ( ) and the adiabatic ionization energy (IE) of the rotamer are determined to be 33 959±3 and 65 326±5 cm, respectively, and those of the rotamer are determined to be 34102±3 and 65 471±5 cm, respectively. Density functional theory (DFT) calculations confirm that both the and rotamers of 3ClTA are stable and coexist in their respective S, S, and D states. Both rotamers adopt planar structures with being slightly more stable than in the respective S, S, and D states. The conformation, substitution, and isotope effects on the molecular structure, active vibrations, and electronic transition and ionization energies of 3ClTA are analyzed.

对邻氯硫代苯甲醚（oClTA）和间氯硫代苯甲醚（3ClTA）测量了共振增强双光子电离（R2PI）和质量分析阈值电离（MATI）光谱。确定该旋转异构体的第一电子激发能（）和绝热电离能（IE）分别为33959±3和65326±5 cm⁻¹，该旋转异构体的分别为34102±3和65471±5 cm⁻¹。密度泛函理论（DFT）计算证实，3ClTA的和旋转异构体都是稳定的，并以各自的S、S和D状态共存。两种旋转异构体均采用平面结构，在各自的S、S和D状态下，比略稳定。分析了构象、取代和同位素对3ClTA分子结构、活性振动、电子跃迁和电离能的影响。