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Vibrational shifts of HXeCl in matrix environments
Keisuke Niimi1, Akira Nakayama, Yuriko Ono
1Graduate School of Chemical Sciences and Engineering, Hokkaido University , Sapporo 060-0810, Japan.
Abstract:
The hybrid quantum-classical simulations are performed to investigate the unusual vibrational spectral shifts of a noble-gas hydride HXeCl in matrix environments (in Ne, Ar, Kr, and Xe matrixes). The high-level ab initio calculations at the CCSD(T) level are employed to construct interaction potential energy surfaces between HXeCl and noble-gas atoms (Ne, Ar, Kr, and Xe). The configurations of noble-gas atoms are sampled by the Monte Carlo simulations and the vibrational levels of HXeCl in the presence of the surrounding noble-gas atoms are solved by the DVR approach. It is found that the H-Xe stretching frequencies are blue-shifted from the isolated gas-phase value in all matrix environments and that the relative blue shifts are in good agreement with the experimental results (Ne < Xe < Kr), demonstrating that the explicit treatment of matrix environments around HXeCl is essential to reproduce the observed unusual vibrational shifts.
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