Entropic representation in the theory of molecular electronic structure

2013
journal article
article
dc.abstract.enThe entropic perspective on the molecular electronic structure is investigated. Information-theoretic description of electron probabilities is extended to cover thecomplexamplitudes(wavefunctions)ofquantummechanics.This analysis emphasizes the entropic concepts due to the phase part of electronic states, which generates the probability currentdensity, thus allowing one to distinguish the information content of states generating the same electron density and differing in their current densities. The classical information measures of Fisher and Shannon, due to the probability/density distributions themselves, are supplemented by the nonclassical terms generated by the wave-function phase or the associated probability current. A complementary character of the Fisher and Shannon information measures is explored and the relationship between these classical information densities is derived. It is postulated to characterize also their nonclassical (phase/current-dependent) contributions. The continuity equations of the generalized information densities are examined and the associated nonclassical information sources are identified. The variational rules involving the quantum-generalized Shannon entropy, which generate the stationary and time-dependent Schrödinger equations from the relevant maximum entropy principles, are discussed and their implications for the system “thermodynamic” equilibrium states are examined. It is demonstrated that the lowest, stationary “thermodynamic” state differs from the true ground state of the system, by exhibiting the space-dependent phase, linked to the modulus part of the wave function, and hence also a nonvanishing probability current.pl
dc.affiliationWydział Chemii : Zakład Chemii Teoretycznej im. K. Gumińskiegopl
dc.contributor.authorNalewajski, Roman - 130874 pl
dc.date.accession2019-02-06pl
dc.date.accessioned2015-02-06T07:57:45Z
dc.date.available2015-02-06T07:57:45Z
dc.date.created2012pl
dc.date.issued2013pl
dc.date.openaccess0
dc.description.accesstimew momencie opublikowania
dc.description.number1pl
dc.description.physical297-315pl
dc.description.points25pl
dc.description.versionostateczna wersja wydawcy
dc.description.volume51pl
dc.identifier.doi10.1007/s10910-012-0084-9pl
dc.identifier.eissn1572-8897pl
dc.identifier.issn0259-9791pl
dc.identifier.projectROD UJ / Ppl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/2864
dc.identifier.weblinkhttps://link.springer.com/content/pdf/10.1007%2Fs10910-012-0084-9.pdfpl
dc.languageengpl
dc.language.containerengpl
dc.rightsUdzielam licencji. Uznanie autorstwa 4.0 Międzynarodowa*
dc.rights.licenceCC-BY
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/legalcode.pl*
dc.share.typeinne
dc.subject.enelectronic structure theorypl
dc.subject.enquantum mechanicspl
dc.subject.enSchrödinger equationpl
dc.subject.enthermodynamic statespl
dc.subject.enquantum fisher informationpl
dc.subject.ennonclassical entropypl
dc.subject.enmaximum entropy principlepl
dc.subject.eninformation continuity equationspl
dc.subtypeArticlepl
dc.titleEntropic representation in the theory of molecular electronic structurepl
dc.title.journalJournal of Mathematical Chemistrypl
dc.typeJournalArticlepl
dspace.entity.typePublication
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