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Chemical graph‐theoretic cluster expansions
Author(s) -
Klein D. J.
Publication year - 1986
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560300717
Subject(s) - formalism (music) , coupled cluster , cluster expansion , graph , statistical physics , ab initio , cluster (spacecraft) , consistency (knowledge bases) , boiling point , rate of convergence , computer science , mathematics , theoretical computer science , molecule , physics , thermodynamics , quantum mechanics , discrete mathematics , art , musical , computer network , channel (broadcasting) , visual arts , programming language
A general computationally amenable chemico‐graph‐theoretic cluster expansion method is suggested as a paradigm for incorporation of chemical structure concepts in a systematic manner. The cluster expansion approach is presented in a formalism general enough to cover a variety of empirical, semiempirical, and even ab initio applications. Formally such approaches for the utilization of chemical structure‐related concepts may be viewed as discrete analogues of Taylor series expansions. The efficacy of the chemical structure concepts then is simply bound up in the rate of convergence of the cluster expansions. In many empirical applications, e.g., boiling points, chromatographic separation coefficients, and biological activities, this rate of convergence has been observed to be quite rapid. More note will be made here of quantum chemical applications. Relations to questions concerning size extensivity of energies and size consistency of wave functions are addressed.