Generalized Quadratic Model for Charge Transfer

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-05-13 DOI:10.1039/d5cp00866b

Angel Albavera-Mata, José L. Gázquez, Alberto Vela

引用次数: 0

Abstract

We present a two-parabola interpolation scheme that recognizes the maximum deviation from the exact linear behavior for density functional approximations. The model is based on the second-order Taylor series expansion of the energy as a function of the electron number for a reference chemical species, and it correctly reduces to a linear scheme for density functionals satisfying the ionization theorems. Use of this generalized model results in revised definitions for the electrodonating and electroaccepting powers that correctly diverge for the exact functional. Further application to charge transfer processes using two hydration reactions shows that this new generalization unequivocally distinguishes between electrophilic and nucleophilic reaction mechanisms. This distinction was impossible with previous approximations based on one- and two-parabolas.

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电荷传递的广义二次模型

我们提出了一种双抛物线插值方案，该方案可以识别密度泛函近似中与精确线性行为的最大偏差。该模型基于能量作为参考化学物质电子数函数的二阶泰勒级数展开，并正确地简化为满足电离定理的密度泛函的线性格式。使用这一广义模型的结果是修正了对精确泛函正确发散的供电和接受电功率的定义。进一步应用于两种水化反应的电荷转移过程表明，这一新的概括明确区分了亲电和亲核反应机制。这种区别是不可能与以前的近似基于一个和两个抛物线。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： 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.