Fractional electron number, temperature, and perturbations in chemical reactions

文献情報

出版日 2016-04-29

DOI 10.1039/C6CP00939E

インパクトファクター 3.676

著者

Paul W. Ayers

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要旨

We provide a perspective on the role of non-integer electron number in the density functional theory approach to chemical reactivity (conceptual DFT), emphasizing that it is important to not only treat reagents as open systems, but also as non-isolated systems, in contact with their surroundings. The special case of well-separated reagents is treated in some detail, as is the case where reagents interact strongly. The resulting expressions for the chemical potential of an acid, μacid = −(αI + A)/(1 + α), and a base, μbase = −(I + αA)/(1 + α), elucidate and generalize the assumptions inherent in the chemical potential models of Mulliken (α = 1) and Gazquez, Cedillo, and Vela (α = 3). In the strongly-interacting limit, it is appropriate to model the effects of the environment as a state-specific effective temperature, thereby providing a rigorous justification for the phenomenological effective-temperature model one of the authors previously proposed. The framework for the strongly interacting limit subsumes our model for weakly-interacting subsystems at nonzero temperature, the case of open but otherwise noninteracting subsystems, and the zero-temperature limit.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 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.

Fractional electron number, temperature, and perturbations in chemical reactions

文献情報

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