利用基于原子轨道的线性响应理论计算周期和非周期系统的电偶极极化率

IF 1.5 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Ravi Kumar, Sandra Luber
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引用次数: 0

摘要

在Kohn-Sham密度泛函理论(KS-DFT)框架下,我们提出了基于原子轨道线性响应理论的电偶极极化率计算,同时考虑了非周期和周期边界条件。我们采用T. Helgaker等人提出的优化方案。化学物理学报,327,397(2000):单电子原子轨道密度矩阵。我们对基于原子轨道和先前实现的基于分子轨道的方法计算的静态极化率进行了比较分析。在涉及周期边界条件的计算中,我们使用基于原子轨道算法的电偶极子算子的速度表示实现极化率计算,随后将结果与基于分子轨道算法的berry相公式和速度表示计算结果进行比较。我们在气相中研究了10个中小分子,分析了多达256个水分子的液相体系,以及锐钛矿TiO2和大块WO3的固态结构。从基于氧化铝的求解器得到的所有极化率结果都与基于氧化铝的结果一致。从我们的示例计算中,我们发现基于ao的求解器比基于mo的求解器具有更好的计算扩展性和更少的内存需求,这使得它更适合于非常大的系统。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Electric Dipole Polarizability Calculation for Periodic and Non-Periodic Systems using Atomic-Orbitals-based Linear Response Theory

We present electric dipole polarizability calculations employing atomic-orbitals based linear response theory within the Kohn-Sham Density Functional Theory (KS-DFT) framework, considering both non-periodic and periodic boundary conditions. We adopt the optimization scheme introduced by T. Helgaker et al. in Chemical Physics Letters 327, 397 (2000) for the single-electron atomic-orbitals density matrix. We conduct a comparative analysis between the static polarizability computed using atomic orbitals-based and previously implemented molecular orbitals-based methods. In our calculations involving periodic boundary conditions, we implement polarizability calculation using velocity representation of the electric dipole operator in atomic orbitals-based algorithm, subsequently comparing the results with those computed using the Berry-phase formulation and velocity representation in molecular orbitals-based algorithm. We investigate 10 small and medium-sized molecules in the gas phase, analyze liquid-phase systems with up to 256 water molecules, and the solid-state structures of anatase TiO2 and bulk WO3. All polarizability results obtained from the AO-based solver exhibit good agreement with MO-based results. From our example calculations, we find that the AO-based solver exhibits better computational scaling and less memory demand than the MO-based solvers, which makes it better suited for very large systems.

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来源期刊
Helvetica Chimica Acta
Helvetica Chimica Acta 化学-化学综合
CiteScore
3.00
自引率
0.00%
发文量
60
审稿时长
2.3 months
期刊介绍: Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.
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