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利用单双激发多参考组态相互作用方法获得了LiAl分子基态X1∑+及七个激发态a3∏, A1∏, b3∑+, c3∑+, B1∏, C1∑+, d3∏的势能曲线, 通过势能曲线得到各态的平衡核间距Re, 进而求得绝热激发能和垂直激发能.计算结果表明:c3∑+ 电子态是一个不稳定的排斥态, A1∏态是一个较弱的束缚态, 其余6个电子态均为束缚态; b3∑+与 c3∑+态之间存在预解离现象; 8个电子态分别解离到两个通道, 即Li(2S)+Al(2P0)与Li(2P0)+Al(2P0). 接着将势能曲线拟合到Murrel-Sorbie解析势能函数形式, 据此获得各态的光谱数据:基态X1∑+的平衡键长为0.2863 nm, 谐振频率为316 cm-1, 解离能De为1.03 eV, 激发态a3∏, A1∏, b3∑+, c3∑+, B1∏, C1∑+, d3∏的垂直激发能依次为0.27, 0.83, 1.18, 1.14, 1.62, 1.81, 2.00 eV; 解离能依次为1.03, 0.82, 0.26, 排斥态, 1.54, 1.10, 0.93 eV, 相应谐振频率 ωe为339, 237, 394, 排斥态, 429, 192, 178 cm-1. 通过求解核运动的薛定谔方程找到了J=0时 LiAl分子7个束缚电子态的振动能级和转动惯量.The potential energy curves (PECs) for ground electronic state (X1∑+) and seven excited electronic states (a3∏, A1∏, b3∑+, c3∑+, B1∏, C1∑+, d3∏) of LiAl are obtained using the multi-configuration reference single and double excited configuration interaction method. Equilibrium bond length Re, adiabatic excited energy Te and vertical excited energy Tv are obtained. It is shown that c3∑+ is an unstable repulsive state, A1∏ is a weak bound state and the others are all bound states. Predissociation can be found between b3∑+ and c3∑+ states. Eight electronic states are dissociated along two channels, Li(2S)+Al(2P0) and Li(2P0)+Al(2P0). And then PECs are fitted to analytical Murrell-Sorbie (MS) potential function to deduce the spectroscopic parameters:the Re is 0.2863 nm, ωe is 316 cm-1 and De is 1.03 eV for the ground state; the values of Tv of excited states are 0.27, 0.83, 1.18, 1.14, 1.62, 1.81 and 2.00 eV; the values of De are 1.03, 0.82 and 0.26, repulsive state, 1.54, 1.10, 0.93 eV, and the values of corresponding frequency ωe are 339, 237, 394, repulsive state, 429, 192, 178 cm-1. By solving the radial Schrödinger equation of nuclear motion, the vibration levels, inertial rotation constants (J=0) are reported for the first time.
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Keywords:
- LiAl /
- spectroscopic constants /
- potential energy curves /
- vibrational levels
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[2] Boldyrev A I, Gonzales N, Simons J 1994 J. Phys. Chem. 98 9931
[3] Brock L R, Pilgrim J S, Duncan M A 1994 Chem. Phys. Lett. 230 93
[4] Gutsev G L, Jena P, Bartlett R J 1999 J. Chem. Phys. 110 2928
[5] Ruette F, Sánchez M, Añez R, Bermúdez A, Sierraalta A 2005 J. Mol. Struct. (Theochem) 729 19
[6] Wang J C, Zhai D M, Guo F, Ouyang Y F, Du Y, Feng Y P 2008 Theor. Chem. Account. 121 165
[7] Chen H J, Cheng X L, Tang H Y, Wang Q W, Su X F 2010 Acta Phys. Sin. 59 4556 (in Chinese) [陈恒杰, 程新路, 唐海燕, 王全武, 苏欣芳 2010 物理学报 59 4556]
[8] Chen H J, Tang H Y, Cheng X L, Wang Q W 2010 Acta Phys. -Chim. Sin. 26 740 (in Chinese) [陈恒杰, 唐海燕, 程新路, 王全武 2010 物理化学学报 26 740]
[9] Sun B G, Chen H J, Liu F K, Yang Y H 2011 Acta Chem. Sin. 69 761 (in Chinese) [孙宝光, 陈恒杰, 刘丰奎, 杨耀辉 2011 化学学报 69 761]
[10] Langhoff S R, Davidson E R 1974 Int. J. Quantum Chem. 8 61
[11] Krishnan R, Binkley J S, Seeger R, Pople J A 1980 J. Chem. Phys. 72 650
[12] Mclean A D, Chandler G S 1980 J. Chem. Phys. 72 5639
[13] Dunning Jr T H 1989 J. Chem. Phys. 90 1007
[14] Woon D E, Dunning Jr T H 1993 J. Chem. Phys. 98 1358
[15] Neese F 2012 Revision 2.9.01 February 2012 ORCA–An ab initio, DFT and semiempircal SCF-MO package
[16] Sansonetti J E, Martin W C 2005 J. Phys. Chem. Ref. Data 34 1559
[17] Zhu Z H, Yu H G 1997 Molecular Structure and Potential Energy Function (Beijing:Science Press) (in Chinese) [朱正和, 俞华根 1997 分子结构与势能函数 (北京:科学出版社)]
[18] Liu D M, Zhang S D 2012 Acta Phys. Sin. 61 033101 (in Chinese) [刘东梅, 张树东 2012 物理学报 61 033101]
[19] Shi D H, Wei X, Hui L, Sun J F, Zhu Z L, Liu Y F 2012 Spectro. Acta A 93 367
[20] Shi D H, Li W T, Sun J F, Zhu Z L 2012 Internal. J. Quan. Chem. 1002 1
[21] Le Roy R J 2007 'Level8.0:A Computer Program for Solving the Radial Schrödinger Equation for Bound and Quasibound Levels' University of Waterloo Chemical Physics Research Report No. CP-663
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[1] Boldyrev A I, Simons J, Schleyer P V R 1993 J. Chem. Phys. 99 8793
[2] Boldyrev A I, Gonzales N, Simons J 1994 J. Phys. Chem. 98 9931
[3] Brock L R, Pilgrim J S, Duncan M A 1994 Chem. Phys. Lett. 230 93
[4] Gutsev G L, Jena P, Bartlett R J 1999 J. Chem. Phys. 110 2928
[5] Ruette F, Sánchez M, Añez R, Bermúdez A, Sierraalta A 2005 J. Mol. Struct. (Theochem) 729 19
[6] Wang J C, Zhai D M, Guo F, Ouyang Y F, Du Y, Feng Y P 2008 Theor. Chem. Account. 121 165
[7] Chen H J, Cheng X L, Tang H Y, Wang Q W, Su X F 2010 Acta Phys. Sin. 59 4556 (in Chinese) [陈恒杰, 程新路, 唐海燕, 王全武, 苏欣芳 2010 物理学报 59 4556]
[8] Chen H J, Tang H Y, Cheng X L, Wang Q W 2010 Acta Phys. -Chim. Sin. 26 740 (in Chinese) [陈恒杰, 唐海燕, 程新路, 王全武 2010 物理化学学报 26 740]
[9] Sun B G, Chen H J, Liu F K, Yang Y H 2011 Acta Chem. Sin. 69 761 (in Chinese) [孙宝光, 陈恒杰, 刘丰奎, 杨耀辉 2011 化学学报 69 761]
[10] Langhoff S R, Davidson E R 1974 Int. J. Quantum Chem. 8 61
[11] Krishnan R, Binkley J S, Seeger R, Pople J A 1980 J. Chem. Phys. 72 650
[12] Mclean A D, Chandler G S 1980 J. Chem. Phys. 72 5639
[13] Dunning Jr T H 1989 J. Chem. Phys. 90 1007
[14] Woon D E, Dunning Jr T H 1993 J. Chem. Phys. 98 1358
[15] Neese F 2012 Revision 2.9.01 February 2012 ORCA–An ab initio, DFT and semiempircal SCF-MO package
[16] Sansonetti J E, Martin W C 2005 J. Phys. Chem. Ref. Data 34 1559
[17] Zhu Z H, Yu H G 1997 Molecular Structure and Potential Energy Function (Beijing:Science Press) (in Chinese) [朱正和, 俞华根 1997 分子结构与势能函数 (北京:科学出版社)]
[18] Liu D M, Zhang S D 2012 Acta Phys. Sin. 61 033101 (in Chinese) [刘东梅, 张树东 2012 物理学报 61 033101]
[19] Shi D H, Wei X, Hui L, Sun J F, Zhu Z L, Liu Y F 2012 Spectro. Acta A 93 367
[20] Shi D H, Li W T, Sun J F, Zhu Z L 2012 Internal. J. Quan. Chem. 1002 1
[21] Le Roy R J 2007 'Level8.0:A Computer Program for Solving the Radial Schrödinger Equation for Bound and Quasibound Levels' University of Waterloo Chemical Physics Research Report No. CP-663
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