Radical cation of 1,3-butadiene: Resonance Raman spectrum of deuterated derivatives and improved force field

Tamás Keszthelyi, Robert Wilbrandt, Thomas Bally, Jean Luc Roulin

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Abstract

The resonance Raman spectra of the radical cations of three deuterated derivatives of 1,3-butadiene are reported. Together with the data for the parent compound (cf.: Keszthelyi, T.; Wilbrandt, R.; Bally, T. J. Phys. Chem. 1996, 100, 16843), 22 frequencies of totally symmetric fundamentals are available to complement 29 previously obtained IR data for the same compounds (Tang, W; Zhang, X.-L., Bally, T. J. Phys. Chem. 1993, 97, 4373) and to generate a new and improved scaled quantum mechanical force field of butadiene radical cation based on B3LYP/6-31G* second derivatives. After fitting those with 13 scaling factors, the resulting force field reproduces all 51 observed fundamental vibrations of the four isotopomers with a root-mean-square deviation of 6.03 cm-1 (10.6 cm-1 for the 11 strongly anharmonic C-H/C-D stretches, 3.92 cm-1 for the remaining 40 modes). It allows the first experimentally based prediction of the stretching force constant for the central C-C bond and corrects the previous ones for the terminal C=C stretch. As in the case of the parent compound, evidence is presented for the presence of the s-cis rotamer after ionization whose vibrations are predicted very accurately by scaling a B3LYP/6-31G* force field of cis-butadiene•+ with the optimized scaling factors of the s-trans rotamer.

Original languageEnglish
Pages (from-to)16850-16855
Number of pages6
JournalJournal of physical chemistry
Volume100
Issue number42
DOIs
Publication statusPublished - Jan 1 1996

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ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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