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

O. Anatole Von Lilienfeld, Mark E. Tuckerman

Research output: Contribution to journalArticlepeer-review


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.

Original languageEnglish (US)
Article number154104
JournalJournal of Chemical Physics
Issue number15
StatePublished - 2006

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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