Development of Standard Atomic Wave Functions for Helium through Lawrencium

通过镹开发氦的标准原子波函数

• 批准号: 09640589
• 负责人: KOGA Toshikatsu
• 金额: $ 2.05万
• 依托单位: Muroran Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640589/
• 关键词: Wave functions; Atoms; Electronic states; Hartree-Fock method

Roothaan-Hartree-Fock (RHF) wave functions for the atoms from helium to xenon were published by Clementi and Roetti in 1974. Atomic wave functions for cesium through uranium were published by McLean and McLean in 1981. Wave functions for the atoms after neptunium in the periodic table have not been reported yet. The published wave functions for helium to uranium have been long regarded as the standard reference wave functions in the society of atomic and molecular physics and chemistry. However, the presence of nontrivial errors and insufficient accuracies has been often pointed out for these wave functions.In this project, we have first examined the number of basis functions to be employed, optimized the variational parameters in the basis functions sufficiently, and developed improved atomic RHF wave functions for helium through xenon. The resultant total energies essentially reproduce the Hartree-Fock-limit values. When the properties of the new wave functions have been examined, however, we have detected some inaccuracies in the cusp and long-range asymptotic behaviors. Therefore, we have reconstructed improved atomic wave functions by imposing some correct Hartree-Fock properties as constraints. Our final RHF wave functions can be truly called near-Hartree-Fock wave functions. For the atoms from cesium to lawrencium, we have started from the assignment of the proper ground electronic configuration and term for each atom. Required number of basis functions has been carefully checked, the variational parameters have been sufficiently optimized, and improved wave functions have been developed for all the heavier atoms from cesium to lawrencium. A set of atomic RHF wave functions developed in this project will be a new standard reference in physics and chemistry of atoms and molecules.

Roothaan-Hartree-Fock (RHF) wave functions for the atoms from helium to xenon were published by Clementi and Roetti in 1974. Atomic wave functions for cesium through uranium were published by McLean and McLean in 1981. Wave functions for the atoms after neptunium in the periodic table have not been reported yet. The published wave functions for helium to uranium have been long regarded as the standard reference wave functions in the society of atomic and molecular physics and chemistry. However, the presence of nontrivial errors and insufficient accuracies has been often pointed out for these wave functions.In this project, we have first examined the number of basis functions to be employed, optimized the variational parameters in the basis functions sufficiently, and developed improved atomic RHF wave functions for helium through xenon. The resultant total energies essentially reproduce the Hartree-Fock-limit values. When the properties of the new wave functions have been examined, however, we have detected some inaccuracies in the cusp and long-range asymptotic behaviors. Therefore, we have reconstructed improved atomic wave functions by imposing some correct Hartree-Fock properties as constraints. Our final RHF wave functions can be truly called near-Hartree-Fock wave functions. For the atoms from cesium to lawrencium, we have started from the assignment of the proper ground electronic configuration and term for each atom. Required number of basis functions has been carefully checked, the variational parameters have been sufficiently optimized, and improved wave functions have been developed for all the heavier atoms from cesium to lawrencium. A set of atomic RHF wave functions developed in this project will be a new standard reference in physics and chemistry of atoms and molecules.

项目成果

T.Koga: "Hyperbolic Cosine Functions Applied to Atomic ..." J.Mol.Struct. (Theochem). 451. 1-10 (1998)

T.Koga：“双曲余弦函数应用于原子......”J.Mol.Struct。

H.Tatewaki, T.Koga and H.Takashima: "Contracted Gaussian-Type Basis Functions Revisited.II.Atoms Na through Ar" Theoretical Chemistry Accounts. 96(4). 243-247 (1997)

H.Tatewaki、T.Koga 和 H.Takashima：“重温契约高斯型基函数。II.原子 Na 到 Ar”理论化学说明。

T.Koga: "The Radial Limit of Lithium Revisited" Int.J.Quantum Chem.63(2). 287-290 (1997)

T.Koga：“重新审视锂的径向极限”Int.J.Quantum Chem.63(2)。

T.Koga: "Generalized Exponential Functions Applied to..." Z.Phys.D. 41(2). 111-115 (1997)

T.Koga：“广义指数函数应用于……”Z.Phys.D。

T.Koga: "Generalized Exponential Functions Applied to ..." Z.Phys.D. 41. 111-115 (1997)

T.Koga：“广义指数函数应用于……”Z.Phys.D。