论文标题
频率可极化力场的新框架
A new framework for frequency-dependent polarizable force fields
论文作者
论文摘要
可依赖的频率的频率扩展````'''原子符合的kohn-sham密度函数理论近似于二阶'（acks2）[J.化学物理。提出了141，194114（2014）]，称为ACKS2 $ω$。该方法可以在分配频率依赖性分子响应函数后，对有限系统的动态响应特性进行理论预测。该模型中的参数仅作为电子波函数的预期值进行计算，而硬度矩阵完全从ACKS2重复使用，因为使用绝热近似。数值验证表明，可以使用原子单极和偶极子获得准确的模型。使用ACKS2 $ω$评估了42个有机和无机分子单体的吸收光谱，我们的结果与时间依赖性的DFT计算非常吻合。同样，对于$ C_6 $分散系数的计算，ACKS2 $ω$紧密复制其TDDFT参考。当Acks2 $ω$的参数来自PBE/Aug-CC-PVDZ基态时，它将重现903个有机和无机分子间的实验值，MAPE为3.84 \％。我们的结果证实，ACKS2 $ω$在频率依赖性响应的量子力学描述与计算有效的力场模型之间提供了坚实的联系。
A frequency-dependent extension of the polarizable force field ``Atom-Condensed Kohn-Sham density functional theory approximated to the second-order'' (ACKS2) [J. Chem. Phys. 141, 194114 (2014)] is proposed, referred to as ACKS2$ω$. The method enables theoretical predictions of dynamical response properties of finite systems after a partitioning of the frequency-dependent molecular response function. Parameters in this model are computed simply as expectation values of an electronic wavefunction, and the hardness matrix is entirely reused from ACKS2 as an adiabatic approximation is used. A numerical validation shows that accurate models can already be obtained with atomic monopoles and dipoles. Absorption spectra of 42 organic and inorganic molecular monomers are evaluated using ACKS2$ω$, and our results agree well with the time-dependent DFT calculations. Also for the calculation of $C_6$ dispersion coefficients, ACKS2$ω$ closely reproduces its TDDFT reference. When parameters for ACKS2$ω$ are derived from a PBE/aug-cc-pVDZ ground state, it reproduces experimental values for 903 organic and inorganic intermolecular pairs with an MAPE of 3.84\%. Our results confirm that ACKS2$ω$ offers a solid connection between the quantum-mechanical description of frequency-dependent response and computationally efficient force-field models.
