Investigating the influence of intramolecular bond lengths on the intermolecular interaction of H 2 -AgCl complex: Binding energy, intermolecular vibrations, and isotope effects

Abstract

In this paper, we performed a theoretical study on the influence of intramolecular bond lengths on the intermolecular interactions between H 2 and AgCl molecules. Using four sets of bond lengths for the monomers of H 2 and AgCl, four-dimensional intermolecular potential energy surfaces (PESs) were constructed from ab initio data points at the level of single and double excitation coupled cluster method with noniterative perturbation treatment of triple excitations. A T-shaped global minimum was found on the PES. Interestingly, both the binding energies and Ag-H 2 distances present a linear relationship with the intramolecular bond lengths of H 2 -AgCl. The accuracy of these PESs was validated by the available spectroscopic data via the bound state calculations, and the predicted rotational transition frequencies can reproduce the experimental observations with a root-mean-squared error of 0.0003 cm -1 based on the PES constructed with r(H-H) and r(Ag-Cl) fixed at 0.795 and 2.261 Å, respectively. The intermolecular vibrational modes were assigned unambiguously with a simple pattern by analyzing the wave functions. Isotope effects were also investigated by the theoretical calculations, and the results are in excellent agreement with the available spectroscopic data. The transition frequencies for the isotopolog D 2 -AgCl are predicted with the accuracy of 0.3 MHz.