Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 12, 2015
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Article information


Submitted
29 Jan 2015
Accepted
17 Feb 2015
First published
17 Feb 2015

This article is Open Access

Phys. Chem. Chem. Phys., 2015,17, 7872-7880
Article type
Paper
Author version available

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements