POX(X=1,2)的光谱常数与从头算势能曲线

doi:10.19596/j.cnki.1001-246x.7797

计算物理 ›› 2019, Vol. 36 ›› Issue (1): 106-112.DOI: 10.19596/j.cnki.1001-246x.7797

PO_X(X=1,2)的光谱常数与从头算势能曲线

韩晓琴¹, 肖夏杰²

1. 商丘师范学院电子电气工程学院, 河南商丘 476000;
2. 河南质量工程职业学院, 河南平顶山 467000

收稿日期:2017-11-08 修回日期:2018-01-10 出版日期:2019-01-25 发布日期:2019-01-25
作者简介:韩晓琴(1975-),女,硕士,副教授,主要从事原子与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）及河南省科技攻关计划（102102210037）资助项目

Spectral Constants and ab Initio Potential Energy Curves of PO_X(X=1,2)

HAN Xiaoqin¹, XIAO Xiajie²

1. Department of Physics, Shangqiu Normal College, Shangqiu 476000, Henan, China;
2. Henan Quality Polytechnic, Pingdingshan 467000, Henan, China

Received:2017-11-08 Revised:2018-01-10 Online:2019-01-25 Published:2019-01-25

摘要/Abstract

摘要： 采用从头算的多种方法对PO、PO₂自由基的基态结构进行优化计算，结果表明：使用密度泛函（DFT）方法计算的结果最接近实验值.对PO双原子分子优选6-311G（3df）基组进行计算、扫描并拟合.对PO₂三原子分子优选出6-311+G（3df）方法计算结构参数、谐振频率、离解能及力常数，借助多体项展式理论导出PO₂自由基的势能函数并绘制等值势能图.发现：PO₂自由基的对称伸缩振动和旋转势能图中，在O+PO→OPO反应通道上都有鞍点出现，O原子需要越过0.55 eV的能量才能生成稳定的PO₂自由基.要形成PO₂自由基只能通过两等价的通道越过势垒才能形成.

关键词: PO, PO₂, 光谱常数, 从头算, 势能曲线

Abstract: Many methods are used to optimize possible ground state structures of PO、PO₂ with multi-basis set. It was found that DFT method is the most suitable for calculation of PO,PO₂. For PO free radical, M-S potential energy functional constants are calculated with 6-311G(3df). For PO₂ free radical, equilibrium structure, harmonic frequency, dissociation energy and force constant are calculated with 6-311+G(3df). Potential energy functions of PO₂ are derived from many-body expansion theory. It was pointed out that there is a saddle point in reaction kinetics O+PO→OPO, and a stable PO₂ molecule could be formed as O atom with energy surpassing 0.55 eV. A stable PO₂ molecule could be formed through two equivalent channels over barrier.

Key words: PO, PO₂, spectral constant, ab initio, potential energy curve

中图分类号:

O561.1

韩晓琴, 肖夏杰. PO_X(X=1,2)的光谱常数与从头算势能曲线[J]. 计算物理, 2019, 36(1): 106-112.

HAN Xiaoqin, XIAO Xiajie. Spectral Constants and ab Initio Potential Energy Curves of PO_X(X=1,2)[J]. CHINESE JOURNAL OF COMPUTATIONAL PHYSICS, 2019, 36(1): 106-112.

参考文献

[1] ZHU Z H, YU H G. Molecular structure and molecular potential energy function[M]. Beijing:Science Press, 1997:102.
[2] HAN X Q, XIAO X J, LIU Y F. The ab initio and potential energy curve of OH、OCl and HOCl(1A')[J]. Acta Phys Sin, 2012, 61(16):163101(1-7).
[3] MORRISON M A, SUN Weiguo. Computational methods for electron-molecule collisions[M]. HUO W M, GIANTURCO F A eds. New York:Plenum, 1995.
[4] HUBER K P, HERZBERG G. Molecular spectrum and molecular structure (IV)[M]. New York:Van Nostrand, 1979.
[5] CAI Z L, GERHARD H, ROBERT B. Ab initio study of the electronic spectrum of the PO₂ radical[J]. Chem Phys Letts, 1996, 255:350-356.
[6] LESTE A, ROBERT W. Matrix reactions of oxygen atoms with P₄. Infrared spectra of P₄O, P₂O, PO and PO₂[J]. J Am Chem Soc, 1988, 110:5605-5611.
[7] BREWER L, ROSENBIATT G. Dissociation energies of gaseous metal dioxides[J]. Chem Rev, 1961,61:257-263.
[8] DROWART B J, MYERS C E, SZWAR R, VANDER A A. Determination by the mass spectrometric Knudsen cell method of the atomization energies of the molecules PO and PO₂[J]. J Chem Soc Faraday Trans,1972, 68:1749-1757.
[9] LAWRENCE L, LOHR. A theoretical study of the gaseous oxides phosphorus dioxide (PO₂) and phosphorus monoxide (PO), their anions, and their role in the combustion of phosphorus and phosphine[J]. J Phys Chem, 1984, 88:5569-5574.
[10] KAWAGUCHI K, SAITO S, HIRTOA E, OHASHI N. Far-infrared laser magnetic resonance detection and microwave spectroscopy of the PO₂ radical[J]. J Chem Phys, 1985, 82:4893-4902.
[11] ROBERT W, MATTHEW M. Ledrews absorption spectra of the phosphorus oxide (PO₂ and PO₃) radicals in solid argon[J]. J Phys Chem, 1989, 93:126-129.
[12] STEPHEN A, JARRETT S, LAN H H, Lan R G. Ab initio calculations of the structure and infrared spectrum of PO₂, P₂O and P₄O[J]. Chem Phys, 1990, 140:27-33.
[13] QIAN H B, DAVIES P B, AHMAD I K, HAMILTON P A. Detection of the infrared laser spectrum of the PO₂ radical in the gas phase[J]. Chem Phys Lett,1995, 235:255-259.
[14] MICHAEL A L, KRISTIAN J H, PAUL B D. Infrared diode laser spectroscopy of the ν₃ fundamental band of the PO₂ free radical[J]. J Mole Spect, 2011, 269:61-76.
[15] ZENG H, ZHAO J. Theoretical study of structure and analytic potential energy function for the ground state of PO₂ molecule[J]. Chinese Phys B, 2012, 21:078202
[16] SHI D H, LIU H, SUN J F, ZHU Z L, LIU Y F. Investigations on molecular structure and analytic potential energy function of the AsH(X³Σ^-) and AsH₂(C₂_v,X²B₁) radicals[J]. Acta Phys Sin, 2010.59:227-233.
[17] QI C H, WANG M S, YANG C L, XU Q. Theoretical study of spectroscopic constants and anharmonic force field of PO₂ free radical[J]. J Atom Mol Phy, 2014.31:371-376.
[18] ZHU Z H. Atomic and molecular reaction static[M]. Beijing:Science Press, 1996:156.
[19] ALFREDO A, MIGUEL P. A new functional form to obtain analytical potentials of triatomic molecules[J].J Chem Phys,1992,96:1265-1275.
[20] FRANCISCC J. An ab initio study of the structure and stability of Cl-HOCl anionic complex[J]. Chem Phys Lett,1996,260:485-491.
[21] HAN X Q, JIANG L J, LIU Y F. The structure and potential energy function of MgB and MgB₂(¹A₁)[J]. Acta Phys Sin, 200959:1000.
[22] XIAO X J, HAN X Q, LIU Y F. The structure and potential energy function of XF₂(X=B,N) molecular ground state[J]. Acta Phys Sin, 2011, 60:063102.

PO_X(X=1,2)的光谱常数与从头算势能曲线

Spectral Constants and ab Initio Potential Energy Curves of PO_X(X=1,2)

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POX(X=1,2)的光谱常数与从头算势能曲线

Spectral Constants and ab Initio Potential Energy Curves of POX(X=1,2)

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PO_X(X=1,2)的光谱常数与从头算势能曲线

Spectral Constants and ab Initio Potential Energy Curves of PO_X(X=1,2)