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

• Niimi, Keisuke

• Taketsugu, Tetsuya

• Nakayama, Akira

抄録

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 v(gas) < v(Ne) < v(Xe) < v(Kr) < v(Ar) for HXeCCH and HXeBr, while it is v(gas) < v(Ne) < v(Xe) < v(Ar) < v(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 Delta v(HXeCCH) approximate to Delta v(HXeCl) < Delta v(HXeBr) < Delta v(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.

収録刊行物

• Physical chemistry chemical physics

  Physical chemistry chemical physics 17 (12), 7872-7880, 2015-02-17

  The Royal Society of Chemistry

キーワード

• noble-gas hydride
• matrix shift
• hybrid quantum-classical simulation

詳細情報

• CRID: 1050282813994864768
• NII論文ID: 120005703689
• HANDLE: 2115/60714
• ISSN: 14639076
• 本文言語コード: en
• 資料種別: journal article
• データソース種別:
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  • CiNii Articles