Communication: Reduced density matrices in molecular systems: Grand-canonical electron states

Journal Article · Thu Nov 21 00:00:00 EST 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4832495· OSTI ID:22251400

Miranda-Quintana, Ramón A. ^[1]; Rial, Diego ^[2]

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1. Laboratory of Computational and Theoretical Chemistry, Faculty of Chemistry, University of Havana, Zapata e G y Mazón, 10400 Havana (Cuba)
2. Departamento de Matemática, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and IMAS, CONICET, Ciudad Universitaria, 1428 Buenos Aires (Argentina)

Grand-canonical like descriptions of many electron atomic and molecular open systems which are characterized by a non-integer number of electrons are presented. Their associated reduced density matrices (RDMs) are obtained by introducing the contracting mapping for this type of distributions. It is shown that there is loss of information when connecting RDMs of different order by partial contractions. The energy convexity property of these systems simplifies the description. Consequently, this formulation opens the possibility to a new look for chemical descriptors such as chemical potential and reactivity among others. Examples are presented to discuss the theoretical aspects of this work.

• OSTI ID: 22251400
• Journal Information: Journal of Chemical Physics, Vol. 139, Issue 19; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

97 MATHEMATICAL METHODS AND COMPUTING
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DENSITY MATRIX
DISTRIBUTION
ELECTRONS