论文标题
基础设定校正，以偶联的偶极次数估计
Basis-set correction for coupled-cluster estimation of dipole moments
论文作者
论文摘要
目前的工作提出了一种基于密度功能理论（DFT）的基础校正的方法，以计算波功能理论（WFT）中的分子特性。这种方法允许人们加速非变化WFT方法的任何能量衍生物的基础融合，从而将先前的工作推广到基于DFT的基础校正上，在这种基于DFT的基础基准校正上，只能通过非不同的波浪函数来计算地面态能量[J. J.物理。化学Lett。 10，2931（2019）]或在变异波函数上计算为期望值的属性[J.化学物理。 155，044109（2021）]。这项工作的重点是与单，双重和扰动三重激发（CCSD（t））对耦合群集中偶极矩的基础校正，这是在一组偶极矩上的四个分子上进行数值测试的，该分子均具有覆盖两个阶数的偶极矩。由于基础校正仅依赖于Hartree-fock密度，因此相对于CCSD（T）计算之一，其计算成本很小。数值结果的统计分析表明，相对于通常的CCSD（T）计算，偶极矩的基础收敛明显改善。
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 [J. Phys. Chem. Lett. 10, 2931 (2019)] or properties where computed as expectation values over variational wave functions [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 fourteen 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.
