The maximum occupancy condition for the localized property-optimized orbitals

Literature Information

Publication Date 2019-02-12
DOI 10.1039/C8CP07276K
Impact Factor 3.676
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Abstract

It is shown analytically that the Chemist's Localized Property-optimized Orbitals (CLPOs), which are the localized orbitals obtainable from the results of ab initio calculations by the open-source program JANPA (http://janpa.sourceforge.net/) according to the recently proposed optimal property partitioning condition, form the Lewis structure with nearly maximum possible total electron occupancy. The conditions required for this additional optimality to hold are discussed. In particular, when a single-determinant wavefunction is used to describe the molecular system without a noticeable electron delocalization, CLPOs derived from this wavefunction approximately optimize the same target quantity as the Natural Bond Orbitals (NBOs), establishing in this way the link between the two sets of localized orbitals. The performance of CLPO and NBO methods is compared by using a dataset containing 7101 small molecules, and the relevant methodological features of both methods are discussed.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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