Dissociative photoionization of glycerol and its dimer occurs predominantly via a ternary hydrogen-bridged ion-molecule complex.
The photoionization and dissociative photoionization of glycerol are studied experimentally and theoretically. Time-of-flight mass spectrometry combined with vacuum ultraviolet synchrotron radiation ranging from 8 to 15 eV is used to investigate the nature of the major fragments and their corresponding appearance energies. Deuterium (1,1,2,3,3-D5) and (13)C (2-(13)C) labeling is employed to narrow down the possible dissociation mechanisms leading to the major fragment ions (C3H(x)O2(+), C2H(x)O2(+), C2H(x)O(+), CH(x)O(+)). We find that the primary fragmentation of the glycerol radical cation (m/z 92) occurs only via two routes. The first channel proceeds via a six-membered hydrogen-transfer transition state, leading to a common stable ternary intermediate, comprised of neutral water, neutral formaldehyde, and a vinyl alcohol radical cation, which exhibits a binding energy of ≈42 kcal/mol and a very short (1.4 Å) hydrogen bond. Fragmentation of this intermediate gives rise to experimentally observed m/z 74, 62, 44, and 45. Fragments m/z 74 and 62 both consist of hydrogen-bridged ion-molecule complexes with binding energy >25 kcal/mol, whereas the m/z 44 species lacks such stabilization. This explains why water- or formaldehyde-loss products are observed first. The second primary fragmentation route arises from cleaving the elongated C-C bond. Also for this channel, intermediates comprised of hydrogen-bridged ion-molecule complexes exhibiting binding energies >24 kcal/mol are observed. Energy decomposition analysis reveals that electrostatic and charge-transfer interactions are equally important in hydrogen-bridged ion-molecule complexes. Furthermore, the dissociative photoionization of the glycerol dimer is investigated and compared to the main pathways for the monomeric species. To a first approximation, the glycerol dimer radical cation can be described as a monomeric glycerol radical cation in the presence of a spectator glycerol, thus giving rise to a dissociation pattern similar to that of the monomer.
Department of Chemistry and §Department of Physics, University of California, Berkeley , California 94720, United States.
Franziska
F
Bell
Qiao N
QN
Ruan
Amir
A
Golan
Paul R
PR
Horn
Musahid
M
Ahmed
Stephen R
SR
Leone
Martin
M
Head-Gordon
D002412:Cations; D019281:Dimerization; D005990:Glycerol / Q000737:chemistry / Q000528:radiation effects*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D008027:Light; D008968:Molecular Conformation; D011789:Quantum Theory; D055672:Static Electricity; D013816:Thermodynamics
D002412:Cations; D006859:Hydrogen; D005990:Glycerol