离子对生成反应Li+I2→Li++I2-的理论研究:从头算势能面和反应几率

化学学报 ›› 2004, Vol. 62 ›› Issue (16): 1477-1483. 上一篇下一篇

研究论文

离子对生成反应Li+I₂→Li⁺+I₂^-的理论研究:从头算势能面和反应几率

孙孝敏¹, 张君¹, 冯大诚¹, 蔡政亭¹, 边文生²

1. 山东大学理论化学研究所, 济南, 250100;
2. 中国科学院化学研究所分子反应动力学国家重点实验室, 北京, 100080

投稿日期:2003-10-14 修回日期:2004-04-19 发布日期:2014-02-17
通讯作者: zhtcai@sdu.edu.cn
作者简介:蔡政亭,E-mail:zhtcai@sdu.edu.cn
基金资助:
国家自然科学基金(Nos.20173032,20073024)、高等学校博士点基金资助项目.

Theoretical Study of the Ion-pair Formation Process Li + I₂→Li⁺ + I₂^-: Ab initio PES and Reaction Probability

SUN Xiao-Min¹, ZHANG Jun¹, FENG Da-Cheng¹, CAI Zheng-Ting¹, BIAN Wen-Sheng²

1. Institute of Theoretical Chemistry, Shandong University, Jinan 250100;
2. State Key Labrotaroy of Molecular Reaction Dynamics, Institue of Chemistry, Chinese Academy of Sciences, Beijing 100080

Received:2003-10-14 Revised:2004-04-19 Published:2014-02-17

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摘要/Abstract

采用QCISD(T)方法进行了构型优化及势能面扫描.电荷布居分析采用QCISD,对Li+I₂→Li++I₂^-离子对生成反应进行了系统的从头算理论研究:(1)构筑了两电子态(离子性²B₂态和中性分子2A1态)的完全从头算势能面,找到了两电子态势能面上的最低能量反应途径及两势能曲面的交线,据此确定了离子态与中性分子态之间的最可几交叉半径(R_c^max),计算了该处电子精细结构,得到的电子亲合能和解离能与实验光谱数据相吻合;(2)用Landau-Zener公式计算了离子对生成几率,发现了散射共振态的存在,这一结果与Na+I2→Na⁺+I₂^-体系非常相似,并比较了可得到的实验数据.

关键词: 从头算两态势能面, 离子对生成几率, 非绝热耦合, 散射共振态

For ion-pair formation process Li+I₂→Li ++I₂^-, the ab initio potential energy surfaces (PES) of two electronic states (ionic ²B₂ state and covalent ²A₁ state) were constructed by use of QCISD(T) method.Minimum energy reaction path on each PES and the crossing curve of the two-state PES were abstracted.According to the results, the most probable crossing radius (R_c^max) between the ionic and covalent states was determined, and the fine electronic structure on the crossing point was calculated.The electron affinity of I₂ molecule and the dissociation energy of I₂^- anion and the ionization potential of Li atom obtained from present PES are quite in agreement with the experimental and spectrum data.The ion-pair formation probability was calculated using Landau-Zener formula, and from it the scattering resonance state was found, which is similar to the Na+I₂→Na⁺+I₂^- system.

Key words: ab initio potential energy surface of two electronic states, ion-pair formation probability, nonadiabatic coupling, scattering resonance state

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孙孝敏, 张君, 冯大诚, 蔡政亭, 边文生. 离子对生成反应Li+I₂→Li⁺+I₂^-的理论研究:从头算势能面和反应几率[J]. 化学学报, 2004, 62(16): 1477-1483.

SUN Xiao-Min, ZHANG Jun, FENG Da-Cheng, CAI Zheng-Ting, BIAN Wen-Sheng. Theoretical Study of the Ion-pair Formation Process Li + I₂→Li⁺ + I₂^-: Ab initio PES and Reaction Probability[J]. Acta Chimica Sinica, 2004, 62(16): 1477-1483.

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离子对生成反应Li+I₂→Li⁺+I₂^-的理论研究:从头算势能面和反应几率

Theoretical Study of the Ion-pair Formation Process Li + I₂→Li⁺ + I₂^-: Ab initio PES and Reaction Probability

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