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Molecular grand-canonical ensemble density functional theory and exploration of chemical space

J. Chem. Phys. 125, 154104 (2006); doi:10.1063/1.2338537

Published 18 October 2006

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O. Anatole von Lilienfeld
Department of Chemistry, New York University, New York, New York 10003 and Institute for Pure and Applied Mathematics, University of California Los Angeles, Los Angeles, California 90095

Mark E. Tuckerman
Department of Chemistry, New York University, New York, New York 10003; Institute for Pure and Applied Mathematics, University of California Los Angeles, Los Angeles, California 90095; and Courant Institute of Mathematical Sciences, New York University, New York, New York 10003
We present a rigorous description of chemical space within a molecular grand-canonical ensemble multi-component density functional theory framework. A total energy density functional for chemical compounds in contact with an electron and a proton bath is introduced using Lagrange multipliers which correspond to the energetic response to changes of the elementary particle densities. From a generalized Gibbs-Duhem equation analog, reactivity indices such as the nuclear hardness and a molecular Fukui function, which couples the grand-canonical electronic and nuclear degrees of freedom, are obtained. Maxwell relations between composition particles, ionic displacements, and the external potential are discussed. Numerical results for the molecular Fukui function are presented as well as finite temperature estimates for the oxidation of ammonia. ©2006 American Institute of Physics
History: Received 23 May 2006; accepted 28 July 2006; published 18 October 2006
Permalink: http://link.aip.org/link/?JCPSA6/125/154104/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • YEAR: 2006

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0021-9606 (print)   1089-7690 (online)
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