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Type: Artigo de periódico
Title: Basis Set Selection For The Calculation Of The Ir Fundamental Intensities For 1,1-c 2h 2f 2 And F 2co
Author: Silva A.F.
Soares D.X.
Faria S.H.D.M.
Bruns R.E.
Abstract: The theoretical calculation of the CC, CO and the CF 2 asymmetric stretching infrared intensities of the isoelectronic 1,1-C 2H 2F 2 and F 2CO molecules has resulted in large errors varying from 41.0 to 60.5 km mol -1 or 13.5% to 28.0% of their experimental intensities when using extended 6-311++G(3d,3p) basis set wave-functions at the Moller-Plesset 2 level. For this reason new theoretical intensity results are reported using wave-functions calculated with a large variety of basis sets at both the MP2 and QCISD levels. Accurate intensities were obtained with wave-functions formed from basis sets with polarization functions but without diffuse functions, 6-31G(d,p), 6-31G(2d,2p), 6-31G(3d,3p), 6-311G(d,p) and 6-311G(3d,3p) at both electron correlation levels. Best results for these bands were obtained with the 6-31G(2d,2p) wave-function at the QCISD level providing errors less than 10 km mol -1 and 3.4% of the experimental values. The rms errors for all the 1,1-C 2H 2F 2 and F 2CO intensities at this level are 12.3 and 6.5 km mol -1, respectively. These wave functions at both electron correlation levels also resulted in accurate values for the fundamental intensities of trans-C 2H 2F 2 and cis-C 2H 2F 2 with rms errors of less than 10 km mol -1. Theoretical calculations of the infrared intensities of the 1,1-C 2HDF 2 isotopomer indicate that the experimental determination of the CH symmetric stretching intensity of 1,1-C 2H 2F 2 is probably over-estimated owing to severe band overlap and/or Fermi resonance with the ν 2 + ν 3 combination band. © 2011 Elsevier B.V. All rights reserved.
Rights: fechado
Identifier DOI: 10.1016/j.molstruc.2011.08.053
Date Issue: 2012
Appears in Collections:Unicamp - Artigos e Outros Documentos

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