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Issue 12, 2015
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Matrix site effects on vibrational frequencies of HXeCCH, HXeBr, and HXeI: a hybrid quantum-classical simulation

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Abstract

The matrix shifts of the H–Xe stretching frequency of noble-gas hydrides, HXeCCH, HXeBr, and HXeI in various noble-gas matrices (in Ne, Ar, Kr, and Xe matrices) are investigated via the hybrid quantum-classical simulations. The order of the H–Xe stretching frequencies is found to be ν(gas) < ν(Ne) < ν(Xe) < ν(Kr) < ν(Ar) for HXeCCH and HXeBr, while it is ν(gas) < ν(Ne) < ν(Xe) < ν(Ar) < ν(Kr) for HXeI. This order is anomalous with respect to the matrix dielectric constants, and the calculated results reproduce the experimentally observed shifts quite successfully. We also find that the matrix shifts from the gas-phase values are Δν(HXeCCH) ≈ Δν(HXeCl) < Δν(HXeBr) < Δν(HXeI) in the same noble-gas matrix environments, which implies that the weakly bound molecules exhibit large matrix shifts. The local trapping site is analyzed in detail, and it is shown that a realistic modeling of the surrounding matrix environments is essential to describe the unusual matrix shifts accurately.

Graphical abstract: Matrix site effects on vibrational frequencies of HXeCCH, HXeBr, and HXeI: a hybrid quantum-classical simulation

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Publication details

The article was received on 29 Jan 2015, accepted on 17 Feb 2015 and first published on 17 Feb 2015


Article type: Paper
DOI: 10.1039/C5CP00568J
Citation: Phys. Chem. Chem. Phys., 2015,17, 7872-7880
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    Matrix site effects on vibrational frequencies of HXeCCH, HXeBr, and HXeI: a hybrid quantum-classical simulation

    K. Niimi, T. Taketsugu and A. Nakayama, Phys. Chem. Chem. Phys., 2015, 17, 7872
    DOI: 10.1039/C5CP00568J

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