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Density fitting for three-electron integrals in explicitly correlated electronic structure theory

机译:明确相关电子结构理论中三电子积分的密度拟合

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摘要

The principal challenge in using explicitly correlated wavefunctions for molecules is the evaluation of nonfactorizable integrals over the coordinates of three or more electrons. Immense progress was made in tackling this problem through the introduction of a single-particle resolution of the identity. Decompositions of sufficient accuracy can be achieved, but only with large auxiliary basis sets. Density fitting is an alternative integral approximation scheme, which has proven to be very reliable for two-electron integrals. Here, we extend density fitting to the treatment of all three-electron integrals that appear at the MP2-F12/3*A level of theory. We demonstrate that the convergence of energies with respect to auxiliary basis size is much more rapid with density fitting than with the traditional resolution-of-the-identity approach.
机译:使用分子的显式相关波函数的主要挑战是在三个或更多电子的坐标上评估不可分解积分。通过引入身份的单粒子解决方案,在解决此问题方面取得了巨大进展。可以实现足够准确的分解,但是只能使用较大的辅助基集。密度拟合是一种可选的积分逼近方案,已证明对于两电子积分非常可靠。在这里,我们将密度拟合扩展到MP2-F12 / 3 * A理论水平上出现的所有三电子积分的处理。我们证明,与传统的恒等分辨方法相比,密度拟合的能量相对于辅助基础尺寸的收敛要快得多。

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