Vector parametrization of the N-atom problem in quantum mechanics with non-orthogonal coordinates

被引:50
作者
Iung, C [1 ]
Gatti, F
Viel, A
Chapuisat, X
机构
[1] Univ Montpellier 2, Lab Struct & Dynam Syst Mol & Solides, UMR 5636, F-34095 Montpellier 05, France
[2] Univ Paris 11, Ctr Sci Orsay, Chim Theor Lab, CNRS,URA 0506, F-91405 Orsay, France
关键词
D O I
10.1039/a903466h
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
This article aims to present a general method that enables one to build kinetic energy matrices in getting rid, for the angular coordinates (internal and Eulerian), of the heaviness of differential calculus (for expressing kinetic energy operators) and numerical integration (for calculating matrix elements). Therefore, instead of 3N-3 coordinates, only N-1 radial distances are to be treated as coordinates. In the present formulation, the system is described by any set of n vectors {R-i, i=1, ..., n} and the kinetic energy operator is expressed in term of (n-1) angular momenta {L-i, i=1, ..., n-1} and the total angular momentum J. The formalism proposed is general and gives a remarkably compact expression of the kinetic energy in terms of the angular momenta. This expression allows one to circumvent the seeming angular singularities.
引用
收藏
页码:3377 / 3385
页数:9
相关论文
共 37 条
  • [11] EXACT QUANTUM MOLECULAR HAMILTONIANS .1. APPLICATION TO THE DYNAMICS OF 3 PARTICLES
    CHAPUISAT, X
    NAUTS, A
    BRUNET, JP
    [J]. MOLECULAR PHYSICS, 1991, 72 (01) : 1 - 31
  • [12] A COMMENT ON RECENT PROPOSALS FOR THE CALCULATION OF VIBRATION-ROTATION ENERGIES IN MORE-THAN-3 ATOM MOLECULES
    CHAPUISAT, X
    BELAFHAL, A
    NAUTS, A
    IUNG, C
    [J]. MOLECULAR PHYSICS, 1992, 77 (05) : 947 - 955
  • [13] VECTOR PARAMETRIZATION OF THE N-BODY PROBLEM IN QUANTUM-MECHANICS - POLYSPHERICAL COORDINATES
    CHAPUISAT, X
    IUNG, C
    [J]. PHYSICAL REVIEW A, 1992, 45 (09): : 6217 - 6235
  • [14] EXACT QUANTUM-MECHANICAL VIBRATIONAL KINETIC-ENERGY OPERATOR OF SEQUENTIALLY BONDED MOLECULES IN VALENCE INTERNAL COORDINATES
    CSASZAR, AG
    HANDY, NC
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1995, 102 (10) : 3962 - 3967
  • [15] Davydov A. S., 1965, QUANTUM MECH
  • [16] Vector parametrization of the three-atom problem in quantum mechanics
    Gatti, F
    Iung, C
    Leforestier, C
    Menou, M
    Justum, Y
    Nauts, A
    Chapuisat, X
    [J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 1998, 424 (1-2): : 181 - 199
  • [17] Gatti F, 1998, J MOL STRUC-THEOCHEM, V430, P201, DOI 10.1016/S0166-1280(98)90241-X
  • [18] Vector parametrization of the N-atom problem in quantum mechanics.: I.: Jacobi vectors
    Gatti, F
    Lung, C
    Menou, M
    Justum, Y
    Nauts, A
    Chapuisat, X
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (21) : 8804 - 8820
  • [19] GATTI F, UNPUB J CHEM PHYS
  • [20] GATTI F, IN PRESS J CHEM PHYS