Benchmark Calculations on the Atomization Enthalpy,Geometry and Vibrational Frequencies of UF_6 with Relativistic DFT Methods  

作　　者：肖海 李隽 

机构地区：[1]Institute of Theoretical and Computational Chemistry, Department of Chemistry & Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University,Beijing 100084, China

出　　处：《Chinese Journal of Structural Chemistry》2008年第8期967-974,共8页结构化学（英文）

基　　金：NKBRSF (2006CB932305, 2007CB815200) and NNSFC (20525104).The calculations were partially performed using an HP Itanium2 cluster at Tsinghua National Laboratory for Information Science and Technology

摘　　要：Benchmark calculations on the molar atomization enthalpy, geometry, and vibrational frequencies of uranium hexafluoride （UF6） have been performed by using relativistic density functional theory （DFT） with various levels of relativistic effects, different types of basis sets, and exchange-correlation functionals. Scalar relativistic effects are shown to be critical for the structural properties. The spin-orbit coupling effects are important for the calculated energies, but are much less important for other calculated ground-state properties of closed-shell UF6. We conclude through systematic investigations that ZORA- and RECP-based relativistic DPT methods are both appropriate for incorporating relativistic effects. Comparisons of different types of basis sets （Slater, Gaussian, and plane-wave types） and various levels of theoretical approximation of the exchange-correlation functionals were also made.Benchmark calculations on the molar atomization enthalpy, geometry, and vibrational frequencies of uranium hexafluoride （UF6） have been performed by using relativistic density functional theory （DFT） with various levels of relativistic effects, different types of basis sets, and exchange-correlation functionals. Scalar relativistic effects are shown to be critical for the structural properties. The spin-orbit coupling effects are important for the calculated energies, but are much less important for other calculated ground-state properties of closed-shell UF6. We conclude through systematic investigations that ZORA- and RECP-based relativistic DPT methods are both appropriate for incorporating relativistic effects. Comparisons of different types of basis sets （Slater, Gaussian, and plane-wave types） and various levels of theoretical approximation of the exchange-correlation functionals were also made.

关 键 词：UF6 atomization enthalpy relativistic effect density functional theory 

分 类 号：O642[理学—物理化学]