三氯化硼离子C2A′′2 态光电子谱的理论研究

doi:10.3969/j.issn.1007-5461.2021.05.014

量子电子学报 ›› 2021, Vol. 38 ›› Issue (5): 691-698.doi: 10.3969/j.issn.1007-5461.2021.05.014

• “激光光谱新技术与应用”专辑 • 上一篇

三氯化硼离子C²A′′₂ 态光电子谱的理论研究

宁小寒1, 于同坡1, 陈燕2, 单宝坤1, 周晓国1∗, 刘世林1

1 中国科学技术大学, 合肥微尺度物质科学国家研究中心, 化学物理系, 安徽合肥 230026; 2 中国计量科学研究院, 北京 100013

收稿日期:2021-03-25 修回日期:2021-04-21 出版日期:2021-09-28 发布日期:2021-09-28
通讯作者: E-mail: xzhou@ustc.edu.cn E-mail:xzhou@ustc.edu.cn
作者简介:宁小寒 ( 1997 - ), 女, 山东威海人, 硕士, 主要从事光电离光解离方面的研究。 E-mail: nxh@mail.ustc.edu.cn
基金资助:
Supported by National Key R & D Program of China (国家重点研发计划, 2016YFF0200502), National Natural Science Foundation of China (国家自然科学基金, 21873089, 22073088)

Theoretical study on photoelectron spectrum of BCl⁺ ₃ cation in C²A′′₂ state

NING Xiaohan1, YU Tongpo1, CHEN Yan2, SHAN Baokun1, ZHOU Xiaoguo1∗, LIU Shilin

1 Hefei National Laboratory for Physical Sciences at Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China; 2 National Institute of Metrology, Beijing 100013, China

Received:2021-03-25 Revised:2021-04-21 Published:2021-09-28 Online:2021-09-28

摘要/Abstract

摘要： 应用密度泛函理论对 BCl+ 3 离子 C2A′′ 2 态的电子能谱进行了深入研究。在 aug-cc-pvtz 基组下, 分别使用 PBE0、 !B97XD、 M06-2X 三种泛函优化了中性 BCl3 分子、 BCl+ 3 离子基态 X2A′ 2 以及 C2A′′ 2 态的分子结构, 并计算了相应振动频率和电离过程 BCl3(X1A1) →BCl+ 3 (C2A′′ 2 ) 跃迁的 Franck-Condon 因子, 从而得到了该跃迁对应的拟合电子能谱。通过与已有的高分辨实验电子能谱对比, 实现了 BCl+ 3 离子 C2A′′ 2 态实验光谱的高精度光谱拟合, 进而对实验振动序列做了清晰可靠的归属, 得到 BCl+ 3 离子 C2A′′ 2 态的绝热电离能 AIE、垂直电离能 VIE 分别为 (14.298±0.028) eV、 (14.405±0.028) eV, 从而修正了已报道电离能的错误数据。

关键词: 光谱学, 电离能, 密度泛函理论, 光电离, 电子激发态

Abstract: Density functional theory has been applied to in-depth study on photoelectron spectrum of BCl+ 3 cation in the C2A′′ 2 state. With the aug-cc-pvtz basis set, the geometries of neutral BCl3, BCl+ 3 cation in ground state, X2A′ 2, and an electronically excited state, C2A′′ 2 , are optimized using three theory levels of PBE0, !B97XD and M06-2X. Then the corresponding vibrational frequencies and the Franck-Condon factors of the BCl3(X1A1) → BCl+ 3 (C2A′′ 2 ) transition are calculated, and the photoelectron spectrum is simulated. By comparing with the high-resolution photoelectron spectrum obtained previously in experiment, the photoelectron spectrum of the C2A′′ 2 band is successfully simulated, then reliable assignments for the observed vibrational progression are obtained. Based on these vibrational assignments, the adiabatic ionization energy (AIE) and vertical ionization energy (VIE) for BCl+ 3 cation in the C2A′′ 2 state have been determined directly as AIE(C2A′′ 2 )=(14.298 ±0.028) eV and VIE(C2A′′ 2 )=(14.405 ±0.028) eV, respectively, and their wrong values reported in previous experiments have been corrected.

Key words: spectroscopy, ionization energy, density functional theory, photoionization, electronically excited state

中图分类号:

O644.1

宁小寒, 于同坡, 陈燕, 单宝坤, 周晓国∗, 刘世林. 三氯化硼离子C²A′′₂ 态光电子谱的理论研究[J]. 量子电子学报, 2021, 38(5): 691-698.

NING Xiaohan, YU Tongpo, CHEN Yan, SHAN Baokun, ZHOU Xiaoguo∗, LIU Shilin. Theoretical study on photoelectron spectrum of BCl⁺ ₃ cation in C²A′′₂ state[J]. Chinese Journal of Quantum Electronics, 2021, 38(5): 691-698.

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三氯化硼离子C²A′′₂ 态光电子谱的理论研究

Theoretical study on photoelectron spectrum of BCl⁺ ₃ cation in C²A′′₂ state

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