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B3u-态是O2的最强的三重跃迁（B3u-X3g-） Schumann-Runge（SR）带的上态，SR吸收带在保护地球、阻止紫外辐射等方面起着关键作用.SR连续带的光解离是平流层O原子及O3的主要来源，掌握详细准确的O2分子的电子态势能曲线，有助于对这些光谱现象的深入理解.本文通过MOLPRO 软件，采用包含Davison修正的内收缩的多参考组态相互作用（icMRCI+Q）方法，对O2的B3u-态的势能曲线进行了计算，采用的多参考组态函数来自完全活性空间自洽场计算.首先，采用共价组态构成多参考组态，对和B3u-态对称性相同的四个态进行了态平均计算，发现B3u-态不存在双势阱结构，文献（Spectrochimica Acta Part A： Molecular and Biomolecular Spectroscopy 2014 124 216） 中双势阱的产生是根的振荡（root flipping）造成的，即B3u- 态的势能曲线在核间距约为0.2 nm处跳变到能量相近的23 态的势能曲线上.本文中的态平均计算避免了这种根的振荡.接着，采用完全活性空间组态相互作用的方法计算B3u- 态的势能曲线，通过改变活性空间的轨道组成，发现带有2u轨道电子布居的里德伯组态对B3u-态的束缚态的特征的出现是必不可少的.最后，通过将2u轨道加入到活性空间中，实现将相关的里德伯组态加入到多参考组态，对B3u-态的势能曲线进行了icMRCI+Q计算，得到相较于以往的理论计算与实验值更加相近的势能曲线以及光谱常数.本文探讨里德伯组态贡献的过程为如何确定多参考组态相互作用计算中的参考组态、提高理论计算的准确度提供了可以借鉴的途径.
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关键词:
- O2分子的B3u-态 /
- 多参考组态相互作用 /
- 势能曲线 /
- 光谱常数
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[9] Tatewaki H, Tanaka K, Sasaki F, Obara S, Ohno K, Yoshimine M 1979 Int. J. Quantum Chem. 15 533
[10] Muller T, Dallos M, Lischka H, Dubrovay Z, Szalay P G 2001 Theor. Chem. Acc. 105 227
[11] Liu H, Shi D S, Sun J F, Zhu Z L, Zhang S L 2014 Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 216
[12] Langhoff S R, Davidson E R 1974 Mol. Int. J. Quantum Chem. 8 61
[13] Werner H J, Knowles P J 1984 J. Chem. Phys. 82 5053
[14] Knowles P J, Werner H J 1985 Chem. Phys. Lett. 115 259
[15] Werner H J, Meyer W 1981 J. Chem. Phys. 74 5794
[16] LeRoy R J 2002 University of Waterloo Chemical Physics Research Report CP-655
[17] Woon D E, Dunning T H 1994 J. Chem. Phys. 100 2975
[18] Halkier A, Helgaker T, Jrgensen P, Klopper W, Koch H, Olsen J, Wilson A K 1998 Chem. Phys. Lett. 286 243
[19] Woon D E, Dunning Jr T H 1995 J. Chem. Phys. 103 4572
[20] Jong W D, Harrison R J, Dixon D A 2001 J. Chem. Phys. 114 48
[21] Kiljunen T, Eloranta J, Khriachtchev H K, Pettersson M, Rsnen M 2000 J. Chem.Phys. 112 7475
[22] Yan B, Pan S P, Wang Z G, Yu J H 2005 Acta Phys. Sin. 54 5618 (in Chinese) [闫冰, 潘守甫, 王志刚, 于俊华 2005 物理学报 54 5618]
[23] Minaev B F, Minaeva V A 2001 Phys. Chem. Chem. Phys. 3 720
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[1] Suzuki D, Kato H, Ohkawa M, Anzai K, Tanaka H, Vieira P, Campbell L, Brunger M J 2011 J. Chem. Phys. 134 064311
[2] Krupenie P H 1972 J. Phys. Chem. Ref. Data 1 423
[3] Lewis B R, Gibson S T, Slanger T G, Huestis D L 1999 J. Chem. Phys. 110 11129
[4] Chiu S S, Cheung A S, Finch M, Jamieson M J, Yoshino K, Dalgarno A, Parkinson W H 1992 J. Chem. Phys. 97 1787
[5] Lewis B R, Gibson S T, Dooley P M 1994 J. Chem. Phys. 100 7012
[6] Lewis B R, Berzins L, Carver J H 1986 J. Quant. Spectrosc. Radiat. Transfer 36 209
[7] Saxon R P, Liu B 1977 J. Chem. Phys. 67 5432
[8] Buenker R J, Peyerimhoff S D, Peric M 1976 Chem. Phys. Lett. 42 383
[9] Tatewaki H, Tanaka K, Sasaki F, Obara S, Ohno K, Yoshimine M 1979 Int. J. Quantum Chem. 15 533
[10] Muller T, Dallos M, Lischka H, Dubrovay Z, Szalay P G 2001 Theor. Chem. Acc. 105 227
[11] Liu H, Shi D S, Sun J F, Zhu Z L, Zhang S L 2014 Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 124 216
[12] Langhoff S R, Davidson E R 1974 Mol. Int. J. Quantum Chem. 8 61
[13] Werner H J, Knowles P J 1984 J. Chem. Phys. 82 5053
[14] Knowles P J, Werner H J 1985 Chem. Phys. Lett. 115 259
[15] Werner H J, Meyer W 1981 J. Chem. Phys. 74 5794
[16] LeRoy R J 2002 University of Waterloo Chemical Physics Research Report CP-655
[17] Woon D E, Dunning T H 1994 J. Chem. Phys. 100 2975
[18] Halkier A, Helgaker T, Jrgensen P, Klopper W, Koch H, Olsen J, Wilson A K 1998 Chem. Phys. Lett. 286 243
[19] Woon D E, Dunning Jr T H 1995 J. Chem. Phys. 103 4572
[20] Jong W D, Harrison R J, Dixon D A 2001 J. Chem. Phys. 114 48
[21] Kiljunen T, Eloranta J, Khriachtchev H K, Pettersson M, Rsnen M 2000 J. Chem.Phys. 112 7475
[22] Yan B, Pan S P, Wang Z G, Yu J H 2005 Acta Phys. Sin. 54 5618 (in Chinese) [闫冰, 潘守甫, 王志刚, 于俊华 2005 物理学报 54 5618]
[23] Minaev B F, Minaeva V A 2001 Phys. Chem. Chem. Phys. 3 720
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