Optimizing Molecular Geometries in Strong Magnetic Fields.
Optimizing Molecular Geometries in Strong Magnetic Fields.
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DOI：
10.1021/acs.jctc.0c01297
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发表时间：
2021-04-13
影响因子：
5.5
通讯作者：
Teale AM
中科院分区：
文献类型：
--
作者：
Irons TJP;David G;Teale AM
在Hartree-Fock（HF）和电流密度泛函理论（CDFT）水平上提出了一种有效的几何导数方法，用于强磁场中分子结构的研究.所需的积分导数构造使用混合McMurchie-Davidson和Rys正交的方法，它结合了前者的顺从性，以评估导数积分与后者的效率为基础的高角动量集。除了其应用程序来评估四中心积分的导数，这种方法也适用于梯度使用分辨率的身份近似，使有效的优化分子结构的多电子系统在强磁场下。CDFT的贡献已经实施了广泛的密度泛函，并包括元GGA水平与电流密度相关的贡献和（范围分离）的混合动力车的第一次。说明性的应用程序的OH和苯分子，揭示了丰富和复杂的化学诱导的存在下的外部磁场。强磁场中的几何优化的挑战突出，沿着的要求，仔细分析所得到的电子结构在每个固定点。相关效应的重要性进行检查，在HF和CDFT水平的结果进行比较。目前实施的分子梯度在CDFT水平提供了一个具有成本效益的方法，在强磁场下的分子结构的研究，开辟了许多新的可能性，在这方面的化学研究。
An efficient implementation of geometrical derivatives at the Hartree–Fock (HF) and current-density functional theory (CDFT) levels is presented for the study of molecular structure in strong magnetic fields. The required integral derivatives are constructed using a hybrid McMurchie–Davidson and Rys quadrature approach, which combines the amenability of the former to the evaluation of derivative integrals with the efficiency of the latter for basis sets with high angular momentum. In addition to its application to evaluating derivatives of four-center integrals, this approach is also applied to gradients using the resolution-of-the-identity approximation, enabling efficient optimization of molecular structure for many-electron systems under a strong magnetic field. The CDFT contributions have been implemented for a wide range of density functionals up to and including the meta-GGA level with current-density dependent contributions and (range-separated) hybrids for the first time. Illustrative applications are presented to the OH and benzene molecules, revealing the rich and complex chemistry induced by the presence of an external magnetic field. Challenges for geometry optimization in strong fields are highlighted, along with the requirement for careful analysis of the resulting electronic structure at each stationary point. The importance of correlation effects is examined by comparison of results at the HF and CDFT levels. The present implementation of molecular gradients at the CDFT level provides a cost-effective approach to the study of molecular structure under strong magnetic fields, opening up many new possibilities for the study of chemistry in this regime.
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影响因子：
8.6
作者：
Berdyugina, S. V.;Berdyugin, A. V.;Piirola, V.
通讯作者：
Piirola, V.
影响因子：
4.1
作者：
Carsky, P;Polasek, M
通讯作者：
Polasek, M
影响因子：
3
作者：
BAKER, J
通讯作者：
BAKER, J
影响因子：
3
作者：
BAKER, J
通讯作者：
BAKER, J
DOI：
10.1007/bf02464849
发表时间：
1987-08-01
期刊：
NUOVO CIMENTO DELLA SOCIETA ITALIANA DI FISICA D-CONDENSED MATTER ATOMIC MOLECULAR AND CHEMICAL PHYSICS FLUIDS PLASMAS BIOPHYSICS
影响因子：
--
作者：
COLLE, R;FORTUNELLI, A;SIMONUCCI, S
通讯作者：
SIMONUCCI, S