Hoyer Chad E, Xu Xuefei, Ma Dongxia, Gagliardi Laura, Truhlar Donald G
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455-0431, USA.
J Chem Phys. 2014 Sep 21;141(11):114104. doi: 10.1063/1.4894472.
In this work, we present a method, called the DQ scheme (where D and Q stand for dipole and quadrupole, respectively), for transforming a set of adiabatic electronic states to diabatic states by using the dipole and quadrupole moments to determine the transformation coefficients. It is more broadly applicable than methods based only on the dipole moment; for example, it is not restricted to electron transfer reactions, and it works with any electronic structure method and for molecules with and without symmetry, and it is convenient in not requiring orbital transformations. We illustrate this method by prototype applications to two cases, LiH and phenol, for which we compare the results to those obtained by the fourfold-way diabatization scheme.
在这项工作中，我们提出了一种称为DQ方案（其中D和Q分别代表偶极矩和四极矩）的方法，该方法通过使用偶极矩和四极矩来确定变换系数，从而将一组绝热电子态转换为非绝热态。它比仅基于偶极矩的方法具有更广泛的适用性；例如，它不限于电子转移反应，可与任何电子结构方法配合使用，适用于具有和不具有对称性的分子，并且无需轨道变换，使用方便。我们通过对LiH和苯酚这两种情况的典型应用来说明该方法，并将结果与通过四重非绝热方案获得的结果进行比较。
