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

Acta Chimica Sinica ›› 2004, Vol. 62 ›› Issue (16): 1477-1483. Previous Articles Next Articles

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

Abstract

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

Cite this article

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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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