Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
J Chem Phys. 2011 Mar 7;134(9):094509. doi: 10.1063/1.3554905.
We report full-dimensional, ab initio potential energy and dipole moment surfaces, denoted PES and DMS, respectively, for arbitrary numbers of water monomers. The PES is a sum of 1-, 2-, and 3-body potentials which can also be augmented by semiempirical long-range higher-body interactions. The 1-body potential is a spectroscopically accurate monomer potential, and the 2- and 3-body potentials are permutationally invariant fits to tens of thousands of CCSD(T)/aug-cc-pVTZ and MP2/aug-cc-pVTZ electronic energies, respectively. The DMS is a sum of 1- and 2-body DMS, which are covariant fits to tens of thousands MP2/aug-cc-pVTZ dipole moment data. We present the details of these new 2- and 3-body potentials and then extensive applications and tests of this PES are made to the structures, classical binding energies, and harmonic frequencies of water clusters up to the 22-mer. In addition, we report the dipole moment for these clusters at various minima and compare the results against available and new ab initio calculations.
我们报道了全维、从头算的势能和偶极矩面，分别表示为 PES 和 DMS，适用于任意数量的水分子单体。PES 是 1-、2-和 3-体势的总和，还可以通过半经验的长程高阶相互作用来增强。1 体势是一个光谱准确的单体势，2-和 3-体势是对成千上万的 CCSD(T)/aug-cc-pVTZ 和 MP2/aug-cc-pVTZ 电子能的排列不变拟合。DMS 是 1-和 2-体 DMS 的总和，是对成千上万的 MP2/aug-cc-pVTZ 偶极矩数据的协变拟合。我们介绍了这些新的 2-和 3-体势的细节，然后对这个 PES 进行了广泛的应用和测试，包括水分子团簇的结构、经典结合能和振动频率，最高可达 22 聚体。此外，我们报告了这些团簇在各种最低点的偶极矩，并将结果与现有的和新的从头算计算进行了比较。
