Can Semilocal Approximations to the Embedding Potential Tackle Charge-Transfer-to-Solvent Excitations? An Aqueous Thiocyanate Example.

IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL
Pierre-Olivier Roy,Mingxue Fu,Ronit Sarangi,Anna I Krylov,Tomasz A Wesolowski
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引用次数: 0

Abstract

Frozen-density embedding theory (FDET) provides a formal basis for methods employing density-dependent embedding potentials. FDET-based methods involve approximations concerning: (i) the choice of the approximant for the bifunctional vxctnad[ρA,ρB], (ii) the localization of the embedded wave function, and (iii) the approach used to generate the electron density of the environment. The set of approximations that has been shown to yield highly accurate complexation-induced shifts in vertical excitation energies for valence excitations localized on the chromophore─referred to as the "standard FDET protocol"─is expected to fail if applied to charge-transfer-to-solvent excitations. This work illustrates that such excitations can also be treated using an FDET-based method; however, they require refinement of the approximations used in the standard protocol.
半局部近似的嵌入势能解决电荷转移到溶剂的激发吗?一个水硫氰酸盐的例子。
冷冻密度嵌入理论(FDET)为采用密度相关嵌入势的方法提供了形式化基础。基于fdet的方法涉及以下方面的近似:(i)双功能vxctnad[ρA,ρB]的近似选择,(ii)嵌入波函数的定位,以及(iii)用于生成环境电子密度的方法。对于定位在发色团上的价态激发,一组被称为“标准FDET方案”的近似值已被证明可以产生高度精确的配位诱导的垂直激发能位移,但如果应用于电荷转移到溶剂的激发,预计将失败。这项工作表明,这种激励也可以使用基于fdet的方法来处理;然而,它们需要对标准协议中使用的近似进行改进。
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来源期刊
Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation 化学-物理:原子、分子和化学物理
CiteScore
9.90
自引率
16.40%
发文量
568
审稿时长
1 months
期刊介绍: The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.
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