IDENTITIES, PERTURBATIVE EXPANSIONS, AND RECURSION-RELATIONS FOR MAPPING OPERATORS, EFFECTIVE-HAMILTONIANS, AND EFFECTIVE OPERATORS

被引:12
作者
HURTUBISE, V [1 ]
机构
[1] UNIV CHICAGO,DEPT CHEM,CHICAGO,IL 60637
关键词
D O I
10.1063/1.465803
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 derive perturbation expansions for the mapping operators (k,l) that transform a full Hilbert space time-independent Hamiltonian H and operator A into, respectively, a finite (multidimensional) space effective Hamiltonian h and effective operator a. The eigenvalues of h are identical to some of those of H, and a produces exact matrix elements of A for the corresponding states. Our derivations are substantially both more general and simpler than most literature ones and yield simple linear recursive expressions for k and 1. Both these mapping solutions and new identities involving h, a, k, and l straightforwardly produce new recursive relations for h and the first known recursive a expressions. We apply our results to the Bloch, Kato, and all norm-preserving formalisms, including the canonical one. The new h and a identities are also shown to be suitable for iterative and multireference coupled cluster approaches.
引用
收藏
页码:265 / 276
页数:12
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