Reflections on size-extensivity, size-consistency and generalized extensivity in many-body theory

被引:97
作者
Nooijen, M [1 ]
Shamasundar, KR
Mukherjee, D
机构
[1] Univ Waterloo, Dept Chem, Waterloo, ON N2L 3G1, Canada
[2] Indian Assoc Cultivat Sci, Kolkata 700032, W Bengal, India
关键词
size-extensivity; size-consistency; generalized extensivity; many-body theory;
D O I
10.1080/00268970500083952
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
An overview is presented of the notions of size-extensivity and size-consistency, which play an important role in the discussion of many-body methods in physics and chemistry. We also introduce the concept of generalized extensivity, which has been used before implicitly in the literature, and provide an operational definition, which can be tested numerically in a similar way as size-consistency. A numerical example illustrates the concept of generalized extensivity as applied to the EOM-CCSD, STEOM-CCSD and extended-STEOM-CCSD electronic structure methods for excited states. In another line of thought it is argued that algebraic proofs are often more easily constructed than diagrammatic proofs to demonstrate proper separation into non-interacting fragments. The algebraic line of reasoning is illustrated for single reference methods and applied to discuss separability properties for a variety of Hilbert space multi-reference coupled cluster methods.
引用
收藏
页码:2277 / 2298
页数:22
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