SeOx(x=1,2)的从头算势能曲线和光谱常数

计算物理 ›› 2014, Vol. 31 ›› Issue (3): 357-362.

SeO_x(x=1,2)的从头算势能曲线和光谱常数

韩晓琴

商丘师范学院物理与电气信息学院, 河南商丘 476000

收稿日期:2013-07-01 修回日期:2013-10-29 出版日期:2014-05-25 发布日期:2014-05-25
作者简介:韩晓琴(1975-),女,硕士,讲师,主要从事原子分子结构与动力学研究,E-mail:hanxiaoqin88@163.com
基金资助:
国家自然科学基金(11074160);河南省科技攻关计划(102102210037)资助项目

ab Initio Potential Energy Curves and Spectral Constants of SeO_x(x=1,2)

HAN Xiaoqin

Department of Physics, Shangqiu Normal College, Shangqiu 476000, China

Received:2013-07-01 Revised:2013-10-29 Online:2014-05-25 Published:2014-05-25

摘要/Abstract

摘要： 采用从头算的多种方法和基组优化计算SeO_x(x=1,2)自由基的基态结构、谐振频率及离解能,优选出QCISD(T)/6-311+G(2df)、B3LYP/6-311G(3d2f)方法分别对SeO、SeO₂自由基进行计算,计算结果与实验结果吻合很好.对SeO自由基拟合出Murrell-Sorbie势能函数参数,计算出SeO自由基的光谱常数和力常数.计算出SeO₂自由基力常数,导出SeO₂自由基的多体展式势能函数,发现SeO₂自由基对称伸缩振动势能图中在对称的O+SeO→SeO₂反应通道上有一鞍点,其活化能约为48.24 kJ·mol^-1,O原子需要越过0.5 eV的能垒才能生成SeO₂的稳定结构.

关键词: SeO, SeO₂, 光谱常数, 势能函数

Abstract: Possible ground state structures, harmonic frequency and dissociation energy of SeO_x(x=1,2) free radical are optimized by different methods and base sets included in Gaussian 09. Among them, QCISD(T)/6-311+G(2df) and B3LYP/6-311G(3d2f) are the most suitable for SeO, SeO₂. Calculation results are in good agreement with experiment. For SeO free radical, Murrell-Sorbie potential energy functional constant are calculated, according to which spectral parameters and force constants are shown. It provides basis for further investigation on SeO_x(x=1,2). For SeO₂ free radical, force constants are calculated at the same time. And potential energy functions of SeO₂ are derived with many-body expansion theory. In a symmetric stretching vibration potential energy diagram of SeO₂, saddle points in reaction kinetics O+SeO→SeO₂ in the symmetry dilation potential energy are found. Activation energy is 48.24 kJ·mol^-1. A stable SeO₂ free radical could be formed as O atom with energy surpassing 0.5 eV.

Key words: SeO, SeO₂, spectral constant, potential energy function

中图分类号:

O561.1

韩晓琴. SeO_x(x=1,2)的从头算势能曲线和光谱常数[J]. 计算物理, 2014, 31(3): 357-362.

HAN Xiaoqin. ab Initio Potential Energy Curves and Spectral Constants of SeO_x(x=1,2)[J]. CHINESE JOURNAL OF COMPUTATIONAL PHYSICS, 2014, 31(3): 357-362.

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