Ultrafast resonance-enhanced multiphoton ionization in the azabenzenes: pyridine, pyridazine, pyrimidine, and pyrazine

J Chem Phys. 2012 Feb 7;136(5):054309. doi: 10.1063/1.3682541.

Abstract

We report on the ultrafast photoionization of pyridine, pyridazine, pyrimidine, and pyrazine. These four molecules represent a systematic series of perturbations into the structure of a benzene ring which explores the substitution of a C-H entity with a nitrogen atom, creating a heterocyclic structure. Data are recorded under intense-field, single-molecule conditions. The pulses (50 fs, 800 nm) are focused into the molecular vapor, and ion mass spectra are recorded for intensities of ~10(13) W/cm(2) to ~10(15) W/cm(2). We measure ion yields in the absence of the focal volume effect without the need for deconvolution of the data. For all targets, stable singly- and doubly-charged parent ions (C(6-n)H(6-n)N(n)(+(+))) are observed with features suggesting resonance-enhanced ionization. From the intensity dependence of the ion yield, we infer that excitation occurs both through (1)ππ* transitions (remnants of the benzene structure) and through (1)nπ* transitions, the latter being a result of Rydberg-like excitations of the lone pair electrons of the nitrogen atoms. Stability against intense-field fragmentation is also discussed.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Ions
  • Light
  • Models, Molecular
  • Pyrazines / chemistry*
  • Pyridazines / chemistry*
  • Pyridines / chemistry*
  • Pyrimidines / chemistry*

Substances

  • Ions
  • Pyrazines
  • Pyridazines
  • Pyridines
  • Pyrimidines
  • pyridazine
  • pyrimidine