Traore Diata, Toulouse Julien, Giner Emmanuel
Laboratoire de Chimie Théorique, Sorbonne Université and CNRS, F-75005 Paris, France.
J Chem Phys. 2022 May 7;156(17):174101. doi: 10.1063/5.0087794.
The present work proposes an approach to obtain a basis-set correction based on density-functional theory (DFT) for the computation of molecular properties in wave-function theory (WFT). This approach allows one to accelerate the basis-set convergence of any energy derivative of a non-variational WFT method, generalizing previous works on the DFT-based basis-set correction where either only ground-state energies could be computed with non-variational wave functions [Loos et al., J. Phys. Chem. Lett. 10, 2931 (2019)] or properties could be computed as expectation values over variational wave functions [Giner et al., J. Chem. Phys. 155, 044109 (2021)]. This work focuses on the basis-set correction of dipole moments in coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)], which is numerically tested on a set of 14 molecules with dipole moments covering two orders of magnitude. As the basis-set correction relies only on Hartree-Fock densities, its computational cost is marginal with respect to the one of the CCSD(T) calculations. Statistical analysis of the numerical results shows a clear improvement of the basis convergence of the dipole moment with respect to the usual CCSD(T) calculations.
本工作提出了一种基于密度泛函理论（DFT）来获得基组校正的方法，用于在波函数理论（WFT）中计算分子性质。这种方法能够加速非变分WFT方法的任何能量导数的基组收敛，推广了先前基于DFT的基组校正工作，在这些工作中，要么只能用非变分波函数计算基态能量[Loos等人，《物理化学快报》10, 2931 (2019)]，要么可以将性质计算为变分波函数的期望值[Giner等人，《化学物理杂志》155, 044109 (2021)]。本工作聚焦于含单、双和微扰三激发的耦合簇方法[CCSD(T)]中偶极矩的基组校正，并在一组14个分子上进行了数值测试，这些分子的偶极矩跨度达两个数量级。由于基组校正仅依赖于哈特里 - 福克密度，其计算成本相对于CCSD(T)计算而言微不足道。数值结果的统计分析表明，相对于常规的CCSD(T)计算，偶极矩的基组收敛有明显改善。
