Present address: Department of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK. In an Appendix, the photofragment ion yields are compared with the ion yields obtained in collisional activation (CA) experiments, in particular by Kim and McLafferty, in which the primary toluene ion is formed by electron impact. The fragmentation of toluene + (H20}3 to generate (H20}3H + and a benzyl radical takes place by two distinct pathways with generation times 71 < 60 ns and 72 = 480 ns. From the published photoelectron spectra we estimate that at 21.21 eV photon energy, 26.0% of the energy in excess of the first ionization potential is deposited into the parent toluene ion molecular orbitals whose energies lie between its ionization potential and 11.4 eV, which is the onset we observe for the lowest-energy fragmentation process in toluene-h 8 (C 7 H 8 +hν → C 7 H 8 + →C 7 H … title = "A Mass Spectrometry Study of the Fragmentation in Toluene". [2], The driving force of charge site-initiated fragmentation is the inductive effect of the charge site in radical cations. laser induced dissociation which uses laser to induce the ion formation, These reactions are well documented over the decades and fragmentation pattern is useful to determine the molar weight and structural information of the unknown molecule. We investigate the influence of continuum generation on the photofragmentation dynamics of the toluene molecule. White-light-induced fragmentation of toluene. Retrieved from http://link.aps.org/abstract/PRL/v88/e023001. A Mass Spectrometry Study of the Fragmentation in Toluene. The possible energetics, kinetics, and mechanisms for these fragmentations are discussed. The fragmentation of toluene + (H20}3 to generate (H20}3H + and a benzyl radical takes place by two distinct pathways with generation times 71 < 60 ns and 72 = 480 ns. collision-induced dissociation (CID) through collision with neutral molecule, [1][2] Fragmentation that occurs in tandem mass spectrometry experiments has been a recent focus of research as this data helps facilitate the identification of molecules. Supporting data from photoelectron–photoion–photoion coincidence measurements on toluene-h8 at 100 eV were used to detail the contributing dication charge separation processes at high excitation energies. negative electron-transfer dissociation (NETD), author = "Rennie, {E E} and Christopher Johnson and Parker, {John Eric} and Hayes, {M A} and Holland, {D M P} and MacDonald, {M A} and Shaw, {D A} and Shpinkova, {L G}". Agreement NNX16AC86A, Is ADS down? The pure Cn+ carbon ions, C+, C3+, C4+, C5+ and C7+, are observed at high excitation energies and it is shown that they may derive from CnH+ precursors as well as from dication charge separation processes. A Mass Spectrometry Study of the Fragmentation in Toluene. White-Light-Induced Fragmentation of Toluene - NASA/ADS. By sending an 80-fs Ti:sapphire laser beam through a 2-mm-thick CaF2 plate we show that even moderately broadened laser frequency spectra considerably increase the degree of fragmentation, while it is nearly absent without continuum generation. Karl-Ludwig 213, Université de Paris-Sud, F-91405 Orsay, France. ScienceDirect ® is a registered trademark of Elsevier B.V. ScienceDirect ® is a registered trademark of Elsevier B.V. Fragmentation of three isotopic toluene monocations in the 15–100 eV photon energy range. We investigate the influence of continuum generation on the photofragmentation dynamics of the toluene molecule. Depolarization of white light generated by ultrashort laser pulses in optical media. Astrophysical Observatory. Extensive cluster fragmentation (dissociation) is observed even at "threshold ionization energies." The fragments of a molecule cause a unique pattern in the mass spectrum. Where competitive reaction channels are possible, use was made of energy propensity rules, involving product ionization potentials and proton affinities, to propose favored pathways. (or is it just me...), Smithsonian Privacy This occurs in the radical cations with unsaturated functional groups, like ketones, aldehydes, carboxylic acids, esters, amides, olefins, phenylalkanes. A number of similarities and differences to the CA yields obtained at two different ion acceleration potentials are discussed in terms of differences in energy deposition in the parent ion by the photon excitation and CA techniques. The measured broadening of the frequency spectra and the known Raman-active vibrational modes of toluene afford an explanation in terms of a…, Enhanced fragmentation of toluene through linear and nonlinear increase of the focal spot area of an ultrashort laser pulse, Self-action effects in ionization and fragmentation of toluene by femtosecond laser pulses, Chirp and polarization control of femtosecond molecular fragmentation. electron-capture dissociation (ECD) due to capturing of low energy electrons, Rennie, E E ; Johnson, Christopher ; Parker, John Eric ; Hayes, M A ; Holland, D M P ; MacDonald, M A ; Shaw, D A ; Shpinkova, L G. /. Spectral phase effects on nonlinear resonant photochemistry of 1,3-cyclohexadiene in solution. Rules for the basic fragmentation processes are given by Stevenson’s Rule. Fragment ion formation threshold energies, obtained from photoion mass spectrometry measurements, were used to determine possible fragmentation pathways on the basis of reaction thermochemistry. We investigate the influence of continuum generation on the photofragmentation dynamics of the toluene molecule. Cleavage occurs when the radical and an odd electron from the bonds adjacent to the radical migrate to form a bond between the alpha carbon and either the heteroatom or the unsaturated functional group. We investigate the influence of continuum generation on the photofragmentation dynamics of the toluene molecule. By continuing you agree to the use of cookies, Heriot-Watt Research Portal data protection policy, Heriot-Watt Research Portal contact form. We investigate the influence of continuum generation on the photofragmentation dynamics of the toluene molecule. Laser Chemistry, Max Planck Institute of Quantum Optics, Max Planck Society; Kompa, Sigma bond cleavage, radical site-initiated fragmentation, and charge site-initiated fragmentation are few types of simple bond cleavage reactions. The possible energetics, kinetics, and mechanisms for these fragmentations are discussed.