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

O. Anatole Von Lilienfeld, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

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
Volume125
Issue number15
DOIs
StatePublished - 2006

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Elementary particles
Gibbs equations
chemical compounds
Lagrange multipliers
Chemical compounds
elementary particles
Ammonia
Density functional theory
Protons
ammonia
baths
hardness
reactivity
flux density
degrees of freedom
Hardness
analogs
density functional theory
Oxidation
oxidation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Molecular grand-canonical ensemble density functional theory and exploration of chemical space. / Von Lilienfeld, O. Anatole; Tuckerman, Mark.

In: Journal of Chemical Physics, Vol. 125, No. 15, 154104, 2006.

Research output: Contribution to journalArticle

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