Al2O3X2 (X= H, D, T)的电子振动近似方法

杨雷; 谌晓洪; 王玲; 胡连瑞

doi:10.7498/aps.61.232501

摘要

用密度泛函理论在B3LYP/6-311++g (d, p)基组水平上对 Al2O3X2 (X= H, D, T)分子的可能较低能量构型进行了几何优化. 结果表明该分子的基态电子态和对称性为Al2O3X2 (X= H, D, T) (1A') Cs, 计算了氢同位素分子及Al2O3X2 (X= H, D, T)的电子能量E、定容热容CV和熵S. 用电子振动近似方法计算了固体Al2O3的氢化热力学函数 H0, S0, G0 , 以及平衡压力与温度的关系. 当Al2O3吸附氢 (氘,氚)形成固体时, 反应的氢氘氚排代效应的顺序为氚排代氘, 氘排代氢, 与钛等金属与氢及其同位素反应的氢氘氚排代效应的顺序相反. 总体来说, 这种排代效应都非常弱. 随着温度的增加, 这系列反应的氢氘氚排代效应趋于消失.

关键词:

Abstract

The geometric configurations, vibration frequencies and thermodynamics properties of Al2O3X2 (X= H, D, T) molecular clusters with lower energy are optimized using the B3LYP/6-311++g (d, p) method. The changes of entropy, enthalpy and Gibbs free energy of the reactions between Al2O3 and hydrogen (deuterium or tritium) gas are calculated by the solid electron-vibration approximate method and thermodynamic formulae at temperatures of 298, 398, 498, 598, 698, 798, 898, 998 and 1098 K, and then the relationships between the equilibrium pressure of hydrogen (deuterium or tritium) gas and temperature in these reactions are obtained. The results show that the ground state of the gaseous Al2O3H2 is Al2O3X2 (X= H, D, T) (1A') Cs. Hydrogen can be displaced by deuterium; deuterium can be displaced by tritium in the reactions between Al2O3 and X2 with the productions of solid Al2O3X2 which relates to ground gaseous Al2O3X2 with Cs symmetry. This displacement sequence is opposite to that in the reactions between titanium and X2. These displacement effects are very weak, and they are weaker and weaker as the temperature increases.

Keywords:

作者及机构信息

1.
西华大学物理与化学学院, 成都 610039;

2.
西华大学先进计算中心, 成都 610039

基金项目: 四川省科技支撑计划(批准号: 2009PZ0055)和四川省教育厅重点项目(批准号: 10ZA105)资助的课题.

Authors and contacts

1.
School of Physics-Chemistry, Xihua University, Chengdu 610039, China;

2.
Research Center for Advanced Computation, Xihua University, Chengdu 610039, China

Funds: Project supported by the Science Supporting Plan of Sichuan Province, China (Grant No. 2009PZ0055) and the Major Project of Education Department in Sichan Province, China (Grant No. 10ZA105).

参考文献

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施引文献

[1]	Linevsky M J, White D, Mann D E 1964 J. Chem. Phys. 41 542
[2]	Cai M, Carter C C, Miller T A, Bondydey V E 1991 J. Chem. Phys. 95 73
[3]	Desai S R, Wu H, Rohlfing C M, Wang L S 1997 J. Chem. Phys. 106 73
[4]	Serebrennikov L V, Osin S B, Maltsev A A 1982 J. Mol. Struct. 81 25
[5]	Sonchlk S M, Andrews L, Cartson K D 1983 J. Phys. Chem. 87 2004
[6]	Andrews L, Burkholder T R, Yustein J T 1992 J. Phys. Chem. 96 10182
[7]	Bucher P R, Yetter A, Dryer F L, Parr T P, Hanson-Parr D M, Vicenzi E P 1996 26th Symposium (International) on Combustion, Combustion Institute Pittsburg, PA p1899
[8]	Friedman R, MaCek A 1963 9th Symposium (International) on Combustion, Combustion Institute Pittsburgh, PA p703
[9]	Mao H P, Wang H Y, Ni Y, Xu G L, Ma M Z, Zhu Z H, Tang Y J 2004 Acta Phys. Sin. 53 1766 (in Chinese) [毛华平, 王红艳, 倪羽, 徐国亮, 马美仲, 朱正和, 唐永建 2004 53 1766]
[10]	Mao H P, Wang H Y, Tang Y J, Zhu Z H, Zheng S T 2004 Acta Phys. Sin. 53 37 (in Chinese) [毛华平, 王红艳, 唐永键, 朱正和, 郑少涛 2004 53 37]
[11]	Li X X, Jia T Q, Feng D H, Xu Z Z 2004 Acta Phys. Sin. 53 2154 (in Chinese) [李晓溪, 贾天卿, 冯东海, 徐至展 2004 53 2154]
[12]	Ma C L 2004 Acta Phys. Sin. 53 1952 (in Chinese) [马春兰 2004 53 1952 ]
[13]	Hu Z L 2002 Material for Stored Hydrogen (Beijing: Chemical Industry Press) (in Chinese) [胡子龙 2002 储氢材料 (北京: 化学工业出版社)]
[14]	Cobos C J 2002 J. Mol. Struc. 581 17
[15]	Vacek G, De Leeuw B J, Schaefer III H F 1993 J. Chem. Phys. 98 8704
[16]	Pilgrim J S, Robbins D L, Duncan M A 1993 Chem. Phys. Lett. 202 203
[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]	Alexander O E 1977 Intermediate Quantum Theory of Crystalline Solids (Englewood Cliffs: Prentice-Hall Inc)
[19]	Herzberg G 1979 Molecular Spectra and Molecular Structure VI (Newyork: van Norstrand Reinhold Company)
[20]	Christopher J C 2002 Essentials of Computational Chemistry ( Chichester: John Wiley and Sons)
[21]	Zhu Z H, Liu Y C, Jiang G, Tan M L, Wu S, Jiang G Q, Luo D L 1998 Chin. J. Atomic and Molecular Physics 10 435 (in Chinese) [朱正和, 刘幼成, 蒋刚, 谭明亮, 武胜, 蒋国强, 罗德礼 1998 原子分子 10 435]
[22]	Zhu Z H, Sun Y, Zhong Z K, Zhang L, Wang H Y 2003 Chin. J. Atomic and Molecular Physics 20 525 (in Chinese) [朱正和, 孙颖, 钟正坤, 张莉, 王和义 2003 原子与分子 20 525]
[23]	Shen X H, Zhu Z H, Gao T, Luo S Z 2006 Acta Phys. Sin. 55 3420 (in Chinese) [谌晓洪, 朱正和, 高涛, 罗顺忠 2006 55 3420]
[24]	Shen X H, Gao T, Luo S Z, Ma M Z, Xie A D, Zhu Z H 2006 Acta Phys. Sin. 55 1113 (in Chinese) [谌晓洪, 高涛, 罗顺忠, 马美仲, 谢安东, 朱正和 2006 55 1113]
[25]	Gaussian 03, Revision B 03, Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Montgomery J A, Vreven Jr T, Kudin K N, Burant J C, Millam J M, Iyengar S S, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson G A, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox J E, Hratchian H P, Cross J B, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Ayala P Y, Morokuma K, Voth G A, Salvador P, Dannenberg J J, Zakrzewski V G, Dapprich S, Daniels A D, Strain M C, Farkas O, Malick D K, Rabuck A D, Raghavachari K, Foresman J B, Ortiz J V, Cui Q, Baboul A G, Clifford S, Cioslowski J, Stefanov B B, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin R L, Fox D J, Keith T, Al-Laham M A, Peng C Y, Nanayakkara A, Challacombe M, Gill P M W, Johnson B, Chen W, Wong M W, Gonzalez C, Pople J A, 2003 Gaussian, Inc., Pittsburgh PA

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