Pulsed field ionization-ZEKE spectroscopy of 4-aminobenzonitrile-H2o. Hydrogen-bonding interaction in the amino site

Kenji Sakota, Norifumi Yamamoto, Kazuhiko Ohashi, Morihisa Saeki, Shun Ichi Ishiuchi, Makoto Sakai, Masaaki Fujii, Hiroshi Sekiya

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Abstract

Pulsed field ionization (PFI)-zero-kinetic-energy (ZEKE) photoelectron spectra are measured for 4-aminobenzonitrile (4ABN) and "NH2-donor isomer" of 4ABN-H2O 1: 1 complex in which the oxygen atom of water is bonded to the amino hydrogen (K, Sakota, N. Yamamoto, K. Ohashi, H. Sekiya, M. Saeki, S. Ishiuchi, M. Sakai and M. Fujii, Chem. Phys. Lett., 2001, 341, 70.). We have investigated changes in intermolecular interaction and structure of the NH2-donor isomer upon photoionization. The adiabatic ionization potentials of 4ABN and NH2-donor isomer are determined to be 66 493 and 62 843 cm-1, respectively. The oxygen atom of water is hydrogen bonded to an amino hydrogen atom in the D0 state of NH2 donor isomer as well as in the S1 and S0 states. However, the hydrogen bond is suggested to be much stronger in the D0 state thanin the S1 state from a substantial decrease (3650 cm-1) in the adiabatic potential due to the formation of a hydrogen bond. Normal mode analysis has been made for the intermolecular vibrations in the D0 state with the aid of density functional theory calculations at the B3LYP/aug-cc-pVDZ level. The observation of a prominent progression of the intermolecular stretch mode in the PFI-ZEKE spectrum via the electronic origin of the S1-S0 transition is consistent with the increased hydrogen bond strength in the D0 state.

Original languageEnglish
Pages (from-to)1775-1779
Number of pages5
JournalPhysical Chemistry Chemical Physics
Volume5
Issue number9
DOIs
Publication statusPublished - May 1 2003

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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