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采用Davidson修正的内收缩多参考组态相互作用方法(MRCI+Q)及相关一致基aug-cc-pV5Z和aug-cc-pVQZ分别计算了SiSe分子X1Σ+和A1Π电子态的势能曲线. 为提高势能曲线的计算精度, 利用两点总能量外推公式, 将两个电子态的势能曲线外推至完全基组极限, 并对其进行了标量相对论修正, 相对论效应是在cc-pV5Z基组水平下使用三级Douglas-Kroll-Hess哈密顿算符计算的. 利用MRCI+Q/Q5+DK理论水平的势能曲线获得了这两个态的光谱常数(Te, De, Re, ωe, ωexe, ωeye, Be和αe)和J=0时前30个振动态的Bυ和Dυ等分子常数. 其值与已有的实验结果非常一致. 本文得到的光谱常数和分子常数达到了很高精度, 能为进一步的光谱实验和理论研究提供可靠参考.
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关键词:
- 势能曲线 /
- 基组外推和标量相对论修正 /
- 光谱常数 /
- 分子常数
The potential energy curves (PECs) of X1Σ+ and A1Π electronic states of the SiSe molecule are calculated using the internally contracted multireference configuration interaction approach with the Davidson modification (MRCI+Q) with the correlation-consistent basis sets, aug-cc-pV5Z and aug-cc-pVQZ. In order to improve the quality of the PEC, the PEC is extrapolated to the complete basis set limit by the two-point total-energy extrapolation scheme; and the scalar relativistic correction is included. Scalar relativistic correction calculations are carried out using the third-order Douglas-Kroll Hamiltonian approximation at the level of a cc-pV5Z basis set. The spectroscopic parameters (Te, De, Re, ωe, ωexe, ωeye, Be and αe) of two states are calculated. The spectroscopic results are compared in detail with those reported in the previous literature. Excellent agreement is found between the present spectroscopic results and the experimental ones. Using the PECs obtained by the MRCI+Q/Q5+DK calculations, the Bυ and Dυ are calculated for each vibrational state of each electronic state, and their values of the first 30 vibrational states are reported for X1Σ+ and A1Π states of 28Si80Se molecule when J=0. Comparison with the measurements demonstrates that the present vibrational manifolds are both reliable and accurate. They should be good predictions for the future experimental or theoretical research.-
Keywords:
- potential energy curve /
- extrapolation and scalar relativistic corrections /
- spectroscopic parameter /
- molecular constant
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[2] Vago E E, Barrow R F 1946 Proc. Phys. Sot. 58 538
[3] Vago E E, Barrow R F 1946 Nature 157 77
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[26] Shi D H, Niu X H, Sun J F, Zhu Z L 2012 Acta Phys. Sin. 61 093105 (in Chinese) [施德恒, 牛相宏, 孙金锋, 朱遵略 2012 61 093105]
[27] Xing W, Shi D H, Sun J F, Zhu Z L 2012 Int. J. Mol. Sci. 13 8189
[28] Wang J M, Sun J F, Shi D H, Zhu Z L, Li W T 2012 Acta Phys. Sin. 61 063104 (in Chinese) [王杰敏, 孙金锋, 施德恒, 朱遵略, 李文涛 2012 61 063104]
[29] Liu H, Xing W, Shi D H, Sun J F, Zhu Z L 2012 Acta Phys. Sin. 61 203101 (in Chinese) [刘慧, 邢伟, 施德恒, 孙金锋, 朱遵略 2012 61 203101]
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[1] Barrow R F 1939 Proc. Phys. Sot. 51 267
[2] Vago E E, Barrow R F 1946 Proc. Phys. Sot. 58 538
[3] Vago E E, Barrow R F 1946 Nature 157 77
[4] Hoeft J 1965 Z. Naturforsch. A 20 1122
[5] Bosser G, Lebreton J, Marsigny L 1977 J. Chem. Phys. 77 13
[6] Huber K P, Herzberg G 1979 Molecular Spectra and Molecular Structure (Vol. 4) Constants of Diatomic Molecules (New York: Van Nostrand Reinhold) p608
[7] Lakshminarayana G, Shetty B J 1988 J. Mol. Spectrosc. 130 155
[8] Lakshminarayana G, Shetty B J 1993 J. Mol. Spectrosc. 161 575
[9] Giuliano B M, Bizzocchi L, Grabow J U 2008 J. Mol. Spectrosc. 251 261
[10] Andrews L, Hassanzadeh P, Lanzisera D V, Brabson G D 1996 J. Phys. Chem. 100 16667
[11] Chattopadhyaya S, Das K K 2003 Chem. Phys. Lett. 382 249
[12] Jiao D S, Wang H Y 2009 J. Sichuan. Univ. (Nat. Sci. Ed.) 46 999
[13] Langhoff S R, Davidson E R 1974 Int. J. Quantum Chem. 8 61
[14] Richartz A, Buenker R J, Peyerimhoff S D 1978 Chem. Phys. 28 305
[15] Woon D E, Dunning T H 1993 J. Chem. Phys. 98 1358
[16] Dunning T H 1989 J. Chem. Phys. 90 1007
[17] Mller T 2006 NIC Series 31 19
[18] Reiher M, Wolf A 2004 J. Chem. Phys. 121 2037
[19] Wolf A, Reiher M, Hess B A 2002 J. Chem. Phys. 117 9215
[20] Hirata S, Yanai T, Jong W A, Nakajima T, Hirao K 2004 J. Chem. Phys. 120 3297
[21] Krogh J W, Lindh R, Malmqvist P {\AA}, Roos B O, Veryazov V, Widmark P O 2009 User Manual (Molcas Version 7.4) (Lund: Lund University)
[22] Shi D H, Xing W, Zhang X N, Sun J F, Zhu Z L, Liu Y F 2011 Comput. Theor. Chem. 969 17
[23] Shi D H, Xing W, Sun J F, Zhu Z L, Liu Y F 2011 Comput. Theor. Chem. 966 44
[24] Wang J M, Feng H Q, Sun J F, Shi D H 2012 Chin. Phys. B 21 023102
[25] Wang J M, Zhang L, Shi D H, Zhu Z L, Sun J F 2012 Acta Phys. Sin. 61 153105 (in Chinese) [王杰敏, 张蕾, 施德恒, 朱遵略, 孙金锋 2012 61 153105]
[26] Shi D H, Niu X H, Sun J F, Zhu Z L 2012 Acta Phys. Sin. 61 093105 (in Chinese) [施德恒, 牛相宏, 孙金锋, 朱遵略 2012 61 093105]
[27] Xing W, Shi D H, Sun J F, Zhu Z L 2012 Int. J. Mol. Sci. 13 8189
[28] Wang J M, Sun J F, Shi D H, Zhu Z L, Li W T 2012 Acta Phys. Sin. 61 063104 (in Chinese) [王杰敏, 孙金锋, 施德恒, 朱遵略, 李文涛 2012 61 063104]
[29] Liu H, Xing W, Shi D H, Sun J F, Zhu Z L 2012 Acta Phys. Sin. 61 203101 (in Chinese) [刘慧, 邢伟, 施德恒, 孙金锋, 朱遵略 2012 61 203101]
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