Open AccessInfrared Multiple Photon Dissociation Action Spectroscopy and Theoretical Studies of Triethyl Phosphate Complexes: Effects of Protonation and Sodium Cationization on Structure
Author(s) -
B. Scott Fales,
N. O. Fujamade,
Jos Oomens,
M. T. Rodgers
Publication year - 2011
Publication title -
journal of the american society for mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.961
H-Index - 127
eISSN - 1879-1123
pISSN - 1044-0305
DOI - 10.1007/s13361-011-0208-7
Subject(s) - infrared multiphoton dissociation , chemistry , protonation , mass spectrometry , dissociation (chemistry) , infrared spectroscopy , spectroscopy , fourier transform ion cyclotron resonance , bond dissociation energy , ion , electrospray ionization , photochemistry , analytical chemistry (journal) , fourier transform infrared spectroscopy , infrared , organic chemistry , physics , chromatography , quantum mechanics , optics
The gas-phase structures of protonated and sodium cationized complexes of triethyl phosphate, [TEP + H](+) and [TEP + Na](+), are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy using tunable IR radiation generated by a free electron laser, a Fourier transform ion cyclotron resonance mass spectrometer with an electrospray ionization source, and theoretical electronic structure calculations. Measured IRMPD action spectra are compared to linear IR spectra calculated at the B3LYP/6-31 G(d,p) level of theory to identify the structures accessed in the experimental studies. For comparison, theoretical studies of neutral TEP are also performed. Sodium cationization and protonation produce changes in the central phosphate geometry, including an increase in the alkoxy ∠OPO bond angle and shortening of the alkoxy P-O bond. Changes associated with protonation are more pronounced than those produced by sodium cationization.