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Current Physical Chemistry

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ISSN (Print): 1877-9468
ISSN (Online): 1877-9476

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Electron Communications and Correlations in Subsystems

Author(s): Roman F. Nalewajski*

Volume 12, Issue 2, 2022

Published on: 10 May, 2022

Page: [95 - 116] Pages: 22

DOI: 10.2174/1877946812666220211150808

Abstract

The quantum entanglement of molecular fragments in reactive systems is approached. The "external" (inter-fragment) and “internal” (intra-fragment) correlation energies are expressed in terms of the DFT average correlation holes resulting from the coupling constant integration of the scaled electron repulsion terms in the electronic Hamiltonian. Information networks in the local and configuration resolutions are examined, and their conditional entropy (covalency) and mutual information (iconicity) descriptors are summarized. The local channels in the single Slater determinant approximation of HF theory are explored in some detail. The multisite events in the bond system for the specified molecular state are tackled, cascade (bridge) propagations are examined, and the Fermi (exchange) correlation of HF theory is discussed. The partial density matrices of interacting fragments are introduced, and their role in shaping the ensemble averages of physical observables and effective communications within reactants is examined.

Keywords: Adiabatic connections, coupling constant integration, electron correlation, kohn-sham theory, local communications, reactive systems.

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