Multidimensional Franck-Condon simulations of photodetachment spectra for the formate-water cluster anion: Investigating H atom transfer along the HCOOH+OH reaction coordinate

Jingwei Guo, Igor Pugliesi, Klaus Mueller-Dethlefs, Caroline E. H. Dessent

Research output: Contribution to journalArticlepeer-review

Abstract

A new multidimensional Franck-Condon (FC) simulation methodology was applied to an anionic-neutral cluster transition for the first time to investigate the use of photodetachment spectroscopy of the HCOO-center dot H2O anion as a means to study the HCOO center dot H2O and HCOOH center dot OH neutral clusters. For the HCOO-center dot H2O to HCOO center dot H2O transition, vibrationally resolved simulated spectra were obtained across the threshold detachment region, indicating that photodetachment spectroscopy of the respective anionic cluster should provide detailed structural information on the bifurcated HCOO center dot H2O neutral cluster. The simulations predict that the photodetachment spectra should display prominent progressions of both the intermolecular stretch and the in-plane OCO bending mode. In contrast, for the HCOO-center dot H2O to HCOOH center dot OH transition, the vibronic FC simulations resulted in transitions with negligible intensities, despite the fact that the geometries of the respective anionic and neutral systems were similar. The low FC intensities were traced to the large off-diagonal elements of the Duschinsky matrix for this transition, which arise due to the considerable differences in the vibrational wave functions following hydrogen transfer. (c) 2007 American Institute of Physics.

Original languageEnglish
Pages (from-to)-
Number of pages11
JournalJournal of Chemical Physics
Volume127
Issue number23
DOIs
Publication statusPublished - 21 Dec 2007

Keywords

  • ZEKE-PHOTOELECTRON-SPECTROSCOPY
  • AB-INITIO CALCULATIONS
  • DISSOCIATIVE PHOTODETACHMENT
  • GAS-PHASE
  • COMPLEXES
  • PHENOL
  • ACIDS
  • CF2

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