THE ALGEBRA OF EFFECTIVE-HAMILTONIANS AND OPERATORS - TRUNCATED OPERATORS AND COMPUTATIONAL ASPECTS

被引:18
|
作者
HURTUBISE, V [1 ]
FREED, KF [1 ]
机构
[1] UNIV CHICAGO,DEPT CHEM,CHICAGO,IL 60637
来源
JOURNAL OF CHEMICAL PHYSICS | 1993年 / 99卷 / 10期
关键词
D O I
10.1063/1.465673
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
We extend to finite orders of perturbation theory our previous analysis of effective Hamiltonians h and effective operators a which produce, respectively, exact energies and matrix elements of a time-independent operator A for a finite number of eigenstates of a time-independent Hamiltonian H. The validity of various properties is examined here for perturbatively truncated h and a, particularly, the preservation upon transformation to effective operators of commutation relations involving H and/or constants of the motion, of symmetries, and of the equivalence between dipole length and velocity transition moments. We compare formal and computational features of all a definitions and of the more limited Hellmann-Feynman theorem based ''effective operators,'' which provide only diagonal matrix elements of A in special cases. Norm-preserving transformations to effective operators are found to yield a simpler effective operator formalism from both formal and computational viewpoints.
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页码:7946 / 7969
页数:24
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