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Exploring molecular equilibria using quantum information measures
Author(s) -
Nalewajski Roman F.
Publication year - 2013
Publication title -
annalen der physik
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.009
H-Index - 68
eISSN - 1521-3889
pISSN - 0003-3804
DOI - 10.1002/andp.201200230
Subject(s) - statistical physics , atomic orbital , physics , representation (politics) , quantum , quantum state , phase space , quantum mechanics , electron , politics , political science , law
The quantum information‐theoretic description of electron probabilities and currents in molecules is extended. The Harriman‐Zumbach‐Maschke framework of equidensity orbitals is reexamined and the nonclassical Fisher information contribution it generates is used to determine the system equilibrium states for the fixed (ground‐state) electron density/energy. The lowest of such variational “thermodynamic” states can in general exhibit the space‐dependent phase and hence also nonvanishing probability current. The phase/current feature of electronic states in Harriman's representation is emphasized throughout, the probability interpretation of its key constructs is given, and the phase shifts accompanying interactions between the equidensity orbitals are examined. The phase ‐“temperature” concept is introduced as the information‐theoretic descriptor of probability currents in molecules and their fragments.