Cafiero Mauricio, Adamowicz Ludwik
Department of Chemistry, University of Arizona, Tucson, Arizona 85721, USA.
J Chem Phys. 2005 May 8;122(18):184305. doi: 10.1063/1.1891707.
We show that the nonadiabatic (non-Born-Oppenheimer) ground state of a three-nuclei system can be effectively calculated with the use of an explicitly correlated Gaussian basis set with floating centers. Sample calculations performed for the H2D+ system with various basis set sizes show good convergence with respect to both the total energy and the expectation values of the internuclear distances (molecular geometry), the distances between the nuclei and the electrons, and between the electrons. We also provide a derivation of the formulas for one-particle density calculations and some density plots showing the spatial distribution of the H2D+ nuclear and electronic densities.
我们表明，利用具有浮动中心的显式相关高斯基组，可以有效地计算三核系统的非绝热（非玻恩 - 奥本海默）基态。对具有不同基组大小的H2D +系统进行的示例计算表明，在总能量以及核间距（分子几何结构）、核与电子之间的距离以及电子之间的距离的期望值方面都有良好的收敛性。我们还提供了单粒子密度计算公式的推导以及一些密度图，展示了H2D +核密度和电子密度的空间分布。
