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利用原子分子反应静力学推导出AsCl自由基的基态及激发态的理解极限. 采用完全活性空间自洽场和含Davidson 修正的内收缩多参考组态相互作用理论方法, 在aug-cc-pV5Z基组下对AsCl自由基进行结构优化计算及单点能扫描计算. 在AsCl自由基基态势能曲线的基础上, 通过Molcas程序拟合出了AsCl的光谱常数De, Re, e, ee, Be 和e. 通过求解双原子分子核运动的径向Schrdinger方程, 找到了J=0 时该分子基态存在的40个振动态. 针对每一振动态, 计算了其振动能级、转动惯量B和离心畸变常数D, 与现有的实验及其他理论相比较, 本文的光谱参数和分子常数结果更准确.The dissociation limit of AsCl free-radical is correctly determined based on group theory and atomic and molecular statics. Potential energy curves (PECs) for the ground state and several low-lying electronic excited states of AsCl free-radical are calculated using the multi-reference configuration interaction method with the basis set of aug-cc-pV5Z where the Davidson correction is considered as an approximation to full CI. Separation parameters (Re, e, ee, D0, De, Be and e) are evaluated using the PEC of AsCl. Spectroscopic parameters are compared with those reported in the literature, and excellent agreement is found between them. With the PEC of AsCl free-radical, forty vibrational states of AsCl free-radical are predicted when J=0 by numerically solving the radial Schrdinger equation of nuclear notion. For each vibrational state, the vibrational levels and inertial rotation constants are reported.
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Keywords:
- AsCl /
- potential energy function /
- spectroscopic parameter
[1] Basco N, Yee K K 1967 J. Chem. Commun. 1255
[2] Kruse H, Winter R, Fink E H, Wildt J, Zabel F 1984 Chem. Phys. Lett. 111 100
[3] David R Urban, Jennifer Wilcox 2006 J. Phys. Chem. 110 5847
[4] Werner H J, Knowles P J 1988 J. Chem. Phys. 89 5803
[5] Knowles P J, Werner H J 1988 Chem. Phys. Lett. 145 514
[6] Woon D E, Dunning T H 1993 J. Chem. Phys. 98 1358
[7] Dunning T H, Jr 1989 J. Chem. Phys. 90 1007
[8] Zhu Z H 2007 Atomic and Molecular Reaction Statics (Beijing: Science Press) (in Chinese) [朱正和 2007 原子分子反应静力学 (北京: 科学出版社) 第39页]
[9] Werner H J, Knowles P J, Lindh R, Manby F R, Schtz M, Celani P, Korona T, Mitrushenkov A, Rauhut G, Adler T B, Amos R D, Bernhardsson A, Berning A, Cooper D L, Deegan M J O, Dobbyn A J, Eckert F, Goll E, Hampel C, Hetzer G., Hrenar T, Knizia G., Köppl C, Liu Y, Lloyd A W, Mata R A, May A J, McNicholas S J, Me yer W, Mura M E, Nicklass A, Palmieri P, Pflger K, Pitzer R, Reiher M, Schumann U, Stoll H, Stone A J, Tarroni R, Thorsteinsson T, Wang M, Wolf A 2008 A Package of ab Initio Programs
[10] Langhoff S R, Davidson E R 1974 Int. J. Quantum Chem. 861
[11] Krogh J W, Lindh R, Malmqvist P A, Roos B O, Veryazov V, Widmark P O 2009 User Manual Molcas Version 7.4 (Lund: Lund University)
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[1] Basco N, Yee K K 1967 J. Chem. Commun. 1255
[2] Kruse H, Winter R, Fink E H, Wildt J, Zabel F 1984 Chem. Phys. Lett. 111 100
[3] David R Urban, Jennifer Wilcox 2006 J. Phys. Chem. 110 5847
[4] Werner H J, Knowles P J 1988 J. Chem. Phys. 89 5803
[5] Knowles P J, Werner H J 1988 Chem. Phys. Lett. 145 514
[6] Woon D E, Dunning T H 1993 J. Chem. Phys. 98 1358
[7] Dunning T H, Jr 1989 J. Chem. Phys. 90 1007
[8] Zhu Z H 2007 Atomic and Molecular Reaction Statics (Beijing: Science Press) (in Chinese) [朱正和 2007 原子分子反应静力学 (北京: 科学出版社) 第39页]
[9] Werner H J, Knowles P J, Lindh R, Manby F R, Schtz M, Celani P, Korona T, Mitrushenkov A, Rauhut G, Adler T B, Amos R D, Bernhardsson A, Berning A, Cooper D L, Deegan M J O, Dobbyn A J, Eckert F, Goll E, Hampel C, Hetzer G., Hrenar T, Knizia G., Köppl C, Liu Y, Lloyd A W, Mata R A, May A J, McNicholas S J, Me yer W, Mura M E, Nicklass A, Palmieri P, Pflger K, Pitzer R, Reiher M, Schumann U, Stoll H, Stone A J, Tarroni R, Thorsteinsson T, Wang M, Wolf A 2008 A Package of ab Initio Programs
[10] Langhoff S R, Davidson E R 1974 Int. J. Quantum Chem. 861
[11] Krogh J W, Lindh R, Malmqvist P A, Roos B O, Veryazov V, Widmark P O 2009 User Manual Molcas Version 7.4 (Lund: Lund University)
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