原型碳氢化合物多维势能曲线中的非动力相关效应

IF 2 3区 化学 Q4 CHEMISTRY, PHYSICAL
Amir Karton
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引用次数: 0

摘要

我们证明,同时以较小的增量拉伸分子中的所有键,是逐渐增加其多参考特性的系统方法。我们展示了甲烷、乙烷、乙烯和乙炔这四种碳氢化合物的情况,每种碳氢化合物都代表了逐渐复杂的电子结构。随着所有键同时被拉伸,T1、D1 和 %TAE[(T)] 多参量诊断结果也随之增加。随着化学键的拉伸,直至 CCSDTQ 的总雾化能 (TAE) 的后 CCSD(T) 相关分量也在系统地增加。多参考特性的增加程度与电子结构的复杂性相关,其顺序为甲烷→乙烷→乙烯→乙炔。CCSDTQ/CBS 多维势能曲线是评估强相关效应 DFT 方法性能的基准。传统的 DFT 方法 B97-D、TPSS 和 TPSSh 以及双混合 DFT 方法对多参考效应具有更强的鲁棒性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Nondynamical correlation effects in multidimensional potential energy curves of prototypical hydrocarbons

Nondynamical correlation effects in multidimensional potential energy curves of prototypical hydrocarbons
We demonstrate that simultaneously stretching all bonds in a molecule by small increments provides a systematic approach to gradually increasing its multireference character. We show this for four hydrocarbons — methane, ethane, ethylene, and acetylene — each representing a progressively more complex electronic structure. The T1, D1, and %TAE[(T)] multireference diagnostics increase as all the bonds are stretched simultaneously. The post-CCSD(T) correlation components of the total atomization energy (TAE) up to CCSDTQ systematically increase as the bonds are stretched. The extent of the increase in the multireference character correlates with the complexity of the electronic structure in the order methane → ethane → ethylene → acetylene. The CCSDTQ/CBS multidimensional potential energy curves serve as benchmarks for assessing the performance of DFT methods for strong correlation effects. The conventional DFT methods B97-D, TPSS, and TPSSh and double-hybrid DFT methods are more robust toward multireference effects.
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来源期刊
Chemical Physics
Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
4.60
自引率
4.30%
发文量
278
审稿时长
39 days
期刊介绍: Chemical Physics publishes experimental and theoretical papers on all aspects of chemical physics. In this journal, experiments are related to theory, and in turn theoretical papers are related to present or future experiments. Subjects covered include: spectroscopy and molecular structure, interacting systems, relaxation phenomena, biological systems, materials, fundamental problems in molecular reactivity, molecular quantum theory and statistical mechanics. Computational chemistry studies of routine character are not appropriate for this journal.
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