Hydration of a cationic amide group: a ZEKE spectroscopic study of trans-formanilide H2O

S Ullrich, X Tong, G Tarczay, C E H Dessent, K Muller-Dethlefs

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Abstract

The gas-phase structures of the two isomers (N-H...OH2 bonded and C=O...HOH bonded) of the trans-formanilide-water complex have been investigated by two-colour (1 + 1') resonance enhanced multiphoton ionisation (REMPI) and zero electron kinetic energy (ZEKE) spectroscopy. Excitation energies were determined for the S-1 0(0) transitions of trans-formanilide water to be 35787 +/- 0.2 cm(-1) (NH-bound) and 36118 +/- 0.2 cm(-1) ( CO-bound) which correspond to a red shift of 218 cm(-1) and a blue shift of 114 cm(-1), respectively. This is in excellent agreement with recent one-colour measurements of Dickinson et al., J. Chem. Phys. A, 1999, 103, 6938; and Fedorov et al., J. Chem. Phys. A, 2000, 104, 4943. The D-0 0(0) origins of NH-bound and CO-bound trans-formanilide water were observed by ZEKE spectroscopy at 64 225 5 cm(-1) and 64230 +/- 20 cm(-1) corresponding to red shifts of 3182 cm(-1) and 3177 cm(-1), respectively. Both the REMPI and the ZEKE spectra show numerous intermolecular transitions which were assigned on the basis of comparison to similar complexes and to the trans-formanilide monomer. To support these assignments, ZEKE spectra of trans-formanilide water (NH-bound) were recorded via several vibrationally excited S-1 intermediate states, and ab initio CASSCF calculations were also performed.

Original languageEnglish
Pages (from-to)2897-2903
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume4
Issue number13
DOIs
Publication statusPublished - 2002

Keywords

  • CORRELATED MOLECULAR CALCULATIONS
  • GAUSSIAN-BASIS SETS
  • N-PHENYL FORMAMIDE
  • PHOTOELECTRON-SPECTROSCOPY
  • CONFORMATIONAL-ANALYSIS
  • WATER COMPLEXES
  • EXCITED-STATE
  • AB-INITIO
  • CLUSTERS
  • HYDROGEN

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