Carmona-Espíndola Javier, García-Melgarejo Valeria, Núñez-Rojas Edgar, Mendoza Samantha, García Abraham, Gázquez José L, Alejandre José
Departamento de Química, CONAHCYT-Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Ciudad de México 09340, Mexico.
Ares Materials, Inc., 840 F Ave. Suite 103, Plano, Texas 75074, USA.
J Chem Phys. 2024 Oct 14;161(14). doi: 10.1063/5.0224028.
A new population analysis, ADCHα-I, based on the interpolation between the Hirshfeld (H) and the iterative Hirshfeld (H-I) methods through a parameter α and on the atomic dipole moment corrected Hirshfeld (ADCH) methodology is proposed, in combination with the constrained dipole moment density functional theory (CD-DFT) previously developed, to determine the charge distributions of force fields. Following this approach, the electronic density of the isolated molecule is determined for the value of the dipole moment that reproduces the experimental dielectric constant, in order to incorporate through this property the effects of the surrounding molecules in the liquid, and to carry on this information to the molecular simulation, the new population analysis is built to obtain the set of charges that reproduces this dipole moment. By selecting α = 1/2, one is led to charges that are larger than the ones obtained through H and ADCH and smaller than those of H-I and that incorporate, at the local level, information about the response of isolated atoms to donate or to accept charge, which is not considered in ADCH. The results obtained for several liquid properties indicate that the combination of CD-DFT with this population analysis leads to a good description of the charge distributions in force fields used in molecular simulations.
基于通过参数α在Hirshfeld（H）方法和迭代Hirshfeld（H - I）方法之间进行插值，并结合原子偶极矩校正的Hirshfeld（ADCH）方法，提出了一种新的布居分析方法ADCHα - I。该方法与先前开发的约束偶极矩密度泛函理论（CD - DFT）相结合，用于确定力场的电荷分布。按照这种方法，对于能再现实验介电常数的偶极矩值，确定孤立分子的电子密度，以便通过该性质纳入液体中周围分子的影响，并将此信息传递到分子模拟中。构建新的布居分析以获得能再现此偶极矩的电荷集。通过选择α = 1/2，得到的电荷比通过H方法和ADCH方法得到的电荷大，比H - I方法得到的电荷小，并且在局部水平上纳入了孤立原子供体或受体电荷响应的信息，而这在ADCH方法中未被考虑。针对几种液体性质获得的结果表明，CD - DFT与这种布居分析相结合能够很好地描述分子模拟中使用的力场中的电荷分布。
