Equilibrium gas-phase structures of sodium fluoride, bromide, and iodide monomers and dimers

TY - JOUR

T1 - Equilibrium gas-phase structures of sodium fluoride, bromide, and iodide monomers and dimers

AU - Wann, Derek A.

AU - Rankin, David W H

AU - McCaffrey, Philip D.

AU - Martin, Jan M L

AU - Mawhorter, Richard J.

N1 - © American Chemical Society 2014. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

PY - 2014/3/13

Y1 - 2014/3/13

N2 - The alkali halides sodium fluoride, sodium bromide, and sodium iodide exist in the gas phase as both monomer and dimer species. A reanalysis of gas electron diffraction (GED) data collected earlier has been undertaken for each of these molecules using the EXPRESS method to yield experimental equilibrium structures. EXPRESS allows amplitudes of vibration to be estimated and correction terms to be applied to each pair of atoms in the refinement model. These quantities are calculated from the ab initio potential-energy surfaces corresponding to the vibrational modes of the monomer and dimer. Because they include many of the effects associated with large-amplitude modes of vibration and anharmonicity, we have been able to determine highly accurate experimental structures. These results are found to be in good agreement with those from high-level core-valence ab initio calculations and are substantially more precise than those obtained in previous structural studies.

AB - The alkali halides sodium fluoride, sodium bromide, and sodium iodide exist in the gas phase as both monomer and dimer species. A reanalysis of gas electron diffraction (GED) data collected earlier has been undertaken for each of these molecules using the EXPRESS method to yield experimental equilibrium structures. EXPRESS allows amplitudes of vibration to be estimated and correction terms to be applied to each pair of atoms in the refinement model. These quantities are calculated from the ab initio potential-energy surfaces corresponding to the vibrational modes of the monomer and dimer. Because they include many of the effects associated with large-amplitude modes of vibration and anharmonicity, we have been able to determine highly accurate experimental structures. These results are found to be in good agreement with those from high-level core-valence ab initio calculations and are substantially more precise than those obtained in previous structural studies.

UR - http://www.scopus.com/inward/record.url?scp=84896288384&partnerID=8YFLogxK

U2 - 10.1021/jp411202t

DO - 10.1021/jp411202t

M3 - Article

AN - SCOPUS:84896288384

SN - 1089-5639

VL - 118

SP - 1927

EP - 1935

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 10

ER -