W dniach od 2 kwietnia do 5 kwietnia 2024 r. prowadzone będą prace związane z wdrożeniem nowej wersji systemu Repozytorium UJ. Nie będzie możliwe wprowadzanie nowych informacji do repozytorium. Za utrudnienia przepraszamy.
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,
p
-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 corre-
sponding information/entropy sources are identified in the associated continuity equations.
słowa kluczowe w j. angielskim:
chemical bond multiplicities, contragradience bond detectors, classical and nonclassical information contributions, direct/indirect interactions, electronlocalization function, information continuity, entropic probes of electron densities, information theory, quantum information measures
wydział: instytut / zakład / katedra:
Wydział Chemii : Zakład Chemii Teoretycznej im. K. Gumińskiego