Origin of the step structure of molecular exchange–correlation potentials
文献信息
Sviataslau V. Kohut, Alexander M. Polgar, Viktor N. Staroverov
The exact exchange–correlation potential of a stretched heteronuclear diatomic molecule exhibits a localized upshift in the region around the more electronegative atom; by this device the Kohn–Sham scheme ensures that the molecule dissociates into neutral atoms. Baerends and co-workers showed earlier that the upshift originates in the response part of the exchange–correlation potential. We describe a reliable numerical method for constructing the response potential of a given many-electron system and report accurate plots of this quantity. We also demonstrate that the step feature itself can be obtained directly from the interacting wavefunction of the system by computing the so-called average local electron energy. These findings illustrate in previously unavailable detail the mechanism of the formation of the upshift and the role played by static correlation in this process.
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Physical Chemistry Chemical Physics

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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