SnCl2+低电子态的从头算研究

Ab initio study of low-lying electronic states of SnCl2+.

作者信息

Lee Edmond P F, Dyke John M, Chow Wan-ki, Mok Daniel K W, Chau Foo-tim

机构信息

Department of Building Services Engineering, The Hong Kong Polytechnic University, Hung Hom, Hong Kong.

出版信息

J Phys Chem A. 2007 Dec 20;111(50):13193-9. doi: 10.1021/jp073983w. Epub 2007 Nov 23.

DOI:10.1021/jp073983w

PMID:18034464

Abstract

Complete active space self-consistent field (CASSCF), multireference configuration interaction (MRCI), and restricted-spin coupled-cluster singles-doubles with perturbative triples [RCCSD(T)] calculations have been carried out on low-lying doublet and quartet states of SnCl2+, employing basis sets of up to aug-cc-pV5Z quality. Effects of core correlation and off-diagonal spin-orbit interaction on computed vertical ionization energies were investigated. The best theoretical estimate of the adiabatic ionization energy (including zero-point vibrational energy correction) to the X2A1 state of SnCl2+ is 10.093+/-0.010 eV. The first photoelectron band of SnCl2 has also been simulated by employing RCCSD(T)/aug-cc-pV5Z potential energy functions and including Duschinsky rotation and anharmonicity.

摘要

利用高达aug-cc-pV5Z质量的基组，对SnCl2+的低能双峰和四重态进行了完全活性空间自洽场（CASSCF）、多参考组态相互作用（MRCI）以及含微扰三重激发的受限自旋耦合簇单双激发[RCCSD(T)]计算。研究了核心关联和非对角自旋轨道相互作用对计算得到的垂直电离能的影响。对SnCl2+的X2A1态绝热电离能（包括零点振动能校正）的最佳理论估计值为10.093±0.010 eV。还通过采用RCCSD(T)/aug-cc-pV5Z势能函数并考虑杜施insky旋转和非谐性，模拟了SnCl2的第一光电子能带。