高等学校化学学报

高等学校化学学报

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OClO里德堡态激发能的准确预测及其阴离子低能激发态的从头算研究

魏子章1, 李步通1, 潘清江2, 张红星1   

    1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春130023;
    2. 黑龙江大学化学化工与材料学院, 哈尔滨150080
  • 收稿日期:2006-03-31 修回日期:1900-01-01 出版日期:2007-11-10 发布日期:2007-11-10
  • 通讯作者: 张红星

Accurate Prediction of Excited Energy of Rydberg States of OClO and Ab Initio Investigation of Excited States of OClO Anion with a Low Energy

WEI Zi-Zhang1, LI Bu-Tong1, PAN Qing-Jiang2, ZHANG Hong-Xing1*   

    1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023;
    2. School of Chemistry and Materials Science, Heilongjiang University, Haerbin 150080, China
  • Received:2006-03-31 Revised:1900-01-01 Online:2007-11-10 Published:2007-11-10
  • Contact: ZHANG Hong-Xing

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摘要： 采用全活化空间自洽场方法(CASSCF)研究了OClO阴离子7个低能电子态及其自由基的基态. 为了进一步考虑动态电子相关效应, 采用二级多组态微扰理论(CASPT2)获得更加可靠的能量值. 此外, 在ANO-L基组的基础上, 在OClO自由基的电荷中心增加了为研究里德堡态所建立的1s1p1d的波函数, 并应用多组态二级微扰理论(MS-CASPT2)方法获得了里德堡态的准确电子激发能.

关键词: OClO, 全活化空间自洽场方法, 二级多组态微扰理论, 激发态, 里德堡态

Abstract: By using the complete active space self-consistent field (CASSCF) method with large atomic natural orbital (ANO-L) basis set, seven electronic states of the OClO- anion were calculated. The optimized geometry of the ground state with ANO basis set agrees better with the experimental and previous theoretical values. Furthermore, the stable geometries of three singlet and three triplet excited states were obtained. Taking the further correlation effects into account, the second-order perturbation (CASPT2) calculations were carried out for the energetic calibration. Furthermore, the Rydberg states of the OClO radical were investigated by using multiconfigurational CASPT2 (MS-CASPT2) theory under the basis set of ANO-L functions augmented with an adapted 1s1p1d Rydberg functions that have specially been built for this study. Ten electronic excited states were found for the transition from 3b1 electron into the Rydberg orbitals. The 3b1→ns and 3b1→np series agreed excellent with the experimental values, and the assignment of 3b1→3d series supported the results of Marston. Meanwhile, two and four Rydberg states were computed for the transition of 1a2 and 5b2 electron, respectively.

Key words: OCIO, Complete active space self-consistent field(CASSCF), Second-oder perturbation(CASPT2), Excited state, Rydberg state

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