Use of Harriman’s construction in determining molecular equilibrium states

2013
journal article
article
14
cris.lastimport.wos2024-04-09T19:37:27Z
dc.abstract.enInformation-theoretic description of the electron probabilities and cur- rents in molecules is extended to cover the complex amplitudes (wave functions) of quantummechanics.TheclassicalinformationmeasuresofFisherandShannon,dueto the probability/density distributions themselves, are supplemented by the nonclassical terms generated by the wave-function phase or the associated probability current. The previous one-electron development in such an entropic perspective on the molecular electronic structure is extended to cover N-electron states by adopting the Harriman- type framework of equidensity orbitals. This analysis emphasizes the phase part of electronic states, which generates the probability-current density and the associated non-classical entropy contributions, which allow one to distinguish the information content of states generating the same electron density and differing in their current composition. A complementary character of the Fisher and Shannon information measures is explored in the associated vertical (density-constrained) information principles, for determining the equilibrium state corresponding to the fixed ground-state electron density. It is argued that the lowest “thermodynamic” state generally differs from the true ground state of the system, by exhibiting the space-dependent phase and hence also the non-vanishing probability current, linked to the system electron distribution.pl
dc.affiliationWydział Chemii : Zakład Chemii Teoretycznej im. K. Gumińskiegopl
dc.contributor.authorNalewajski, Roman - 130874 pl
dc.date.accession2019-02-06pl
dc.date.accessioned2015-05-13T06:34:49Z
dc.date.available2015-05-13T06:34:49Z
dc.date.issued2013pl
dc.date.openaccess0
dc.description.accesstimew momencie opublikowania
dc.description.number1pl
dc.description.physical369-381pl
dc.description.versionostateczna wersja wydawcy
dc.description.volume51pl
dc.identifier.doi10.1007/s10910-012-0088-5pl
dc.identifier.eissn1572-8897pl
dc.identifier.issn0259-9791pl
dc.identifier.projectROD UJ / Ppl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/6928
dc.identifier.weblinkhttps://link.springer.com/content/pdf/10.1007%2Fs10910-012-0088-5.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.endensity-constrained principlespl
dc.subject.enelectronic structure theorypl
dc.subject.enentropic principles for moleculespl
dc.subject.enHarriman-Zumbach-Maschke constructionpl
dc.subject.ennonclassical information measurespl
dc.subject.eninformation equilibrium statespl
dc.subtypeArticlepl
dc.titleUse of Harriman’s construction in determining molecular equilibrium statespl
dc.title.journalJournal of Mathematical Chemistrypl
dc.typeJournalArticlepl
dspace.entity.typePublication
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