Article ID: CBB001321117

Entropic Concepts in Electronic Structure Theory (2014)

unapi

It is argued that some elusive 'entropic' characteristics of chemical bonds, e.g., bond multiplicities (orders), which connect the bonded atoms in molecules, can be probed using quantities and techniques of Information Theory (IT). This complementary perspective increases our insight and understanding of the molecular electronic structure. The specific IT tools for detecting effects of chemical bonds and predicting their entropic multiplicities in molecules are summarized. Alternative information densities, including measures of the local entropy deficiency or its displacement relative to the system atomic promolecule, and the nonadditive Fisher information in the atomic orbital resolution(called contragradience) are used to diagnose the bonding patterns in illustrative diatomic and polyatomic molecules. The elements of the orbital communication theory of the chemical bond are briefly summarized and illustrated for the simplest case of the two-orbital model. The information-cascade perspective also suggests a novel, indirect mechanism of the orbital interactions in molecular systems, through 'bridges' (orbital intermediates), in addition to the familiar direct chemical bonds realized through 'space', as a result of the orbital constructive interference in the subspace of the occupied molecular orbitals. Some implications of these two sources of chemical bonds in propellanes, -electron systems and polymers are examined. The current-density concept associated with the wave-function phase is introduced and the relevant phase-continuity equation is discussed. For the first time, the quantum generalizations of the classical measures of the information content, functionals of the probability distribution alone, are introduced to distinguish systems with the same electron density, but differing in their current(phase) composition. The corresponding information/entropy sources are identified in the associated continuity equations. [ABSTRACT FROM AUTHOR]

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Authors & Contributors
Alexander, Sarah C.
Henry, Marc
Rodgers, Glen E.
Steiglitz, Ken
Rogers, David M.
Mayo, Lee Allen
Concepts
Philosophy of science
Entropy
Chemistry
Atoms
Atomic structure
Quantum mechanics
Time Periods
21st century
20th century, late
20th century
19th century
20th century, early
18th century
Places
Great Britain
North America
Europe
Institutions
Club of Rome
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