Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway.
Phys Chem Chem Phys. 2012 Jul 14;14(26):9492-9. doi: 10.1039/c2cp40965h. Epub 2012 May 31.
Analytical integral evaluation is a central task of modern quantum chemistry. Here we present a general method for evaluating differentiated integrals over standard Gaussian and mixed Gaussian/plane-wave hybrid orbitals. The main idea is to have a representation of basis sets that is flexible enough to enable differentiated integrals to be reinterpreted as standard integrals over modified basis functions. As an illustration of the method, we report a very simple implementation of Hartree-Fock level geometrical derivatives in finite magnetic fields for gauge-origin independent atomic orbitals, within the London program. As a quantum-chemical application, we optimize the structure of helium clusters and some well-known covalently bound molecules (water, ammonia and benzene) subject to strong magnetic fields.
分析积分评估是现代量子化学的一项核心任务。在这里，我们提出了一种用于评估标准高斯和混合高斯/平面波混合轨道上微分积分的通用方法。主要思想是具有足够灵活的基组表示形式，以使微分积分可以重新解释为修改后的基函数上的标准积分。作为该方法的说明，我们在 London 程序中报告了在无规范原点的原子轨道中，在有限磁场中 Hartree-Fock 水平几何导数的非常简单的实现。作为量子化学应用，我们在强磁场下优化氦团簇和一些众所周知的共价键合分子（水、氨和苯）的结构。
