The kinetics of the H2 (D2) loss from C2H4+ (C2D4+) ions

The unimolecular H2/D2 loss from C2H4+/C2D4+ ions has been investigated in a threshold photoelectron photoion coincidence spectrometer with electron time of flight discrimination. The experiment shows that the reaction takes place on the microsecond timescale, i.e. is metastable right at the threshold. The experimental breakdown curve for d4-ethene is shifted by 103 meV to a higher excitation energy compared to h4-ethene. The entire breakdown curves were simulated based on model k(E) curves. Best agreement between experiment and simulation was observed for threshold values of k(E0)=7.0×105 s-1 for h4-ethene and k(E0)=2.5×104 s-1 for d4-ethene.

[1]  M. Malow,et al.  Distinguishing the formation of C2D+4 ions from C2D+6 (by D2 loss) and from C2D5H+ (by HD loss) in a Reflectron spectrometer , 1998 .

[2]  P. Španěl,et al.  Ions in the terrestrial atmosphere and in interstellar clouds , 1995 .

[3]  K. Weitzel,et al.  ZEKE-PEPICO investigations of dissociation energies in ionic reactions , 1994 .

[4]  A. D. McLean,et al.  New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+. , 1994, Chemical physics letters.

[5]  P. Španěl,et al.  A further investigation of the reaction of C2H+2 with H2 , 1993 .

[6]  E. Herbst,et al.  Calculations of interstellar radiative association rates including tunnelling: the strange case of C2H+2+ H2 , 1993 .

[7]  David Smith The Ion Chemistry of Interstellar Clouds , 1992 .

[8]  S. Horning,et al.  Experimental investigation of radiative association processes as related to interstellar chemistry , 1992 .

[9]  E. Herbst,et al.  Calculations on the rate of the ion–molecule reaction C2H+2+H2→C2H+3+H , 1992 .

[10]  M. Smith,et al.  The gas phase reaction of C2H+2 with H2 below 3 K: The reopening of the bimolecular C2H+3 channel at low energy , 1992 .

[11]  R. Weinkauf,et al.  Reflectron time-of-flight mass spectrometry and laser excitation for the analysis of neutrals, ionized molecules and secondary fragments , 1992 .

[12]  K. Weitzel,et al.  Threshold photoelectron photoion coincidence study of the ethane loss from energy selected pentane ions cooled in a supersonic expansion , 1991 .

[13]  K. Weitzel,et al.  The rates of HCl loss from energy‐selected ethylchloride ions: A case of tunneling through an H‐atom transfer barrier , 1991 .

[14]  K. Weitzel,et al.  Shifts in photoionization fragmentation onsets. A direct measure of cooling in a supersonic molecular beam , 1991 .

[15]  N. Adams,et al.  A brief review of interstellar ion chemistry , 1989 .

[16]  E. Ferguson,et al.  The heat of formation of C3H2 , 1984 .

[17]  M. Desouter-Lecomte,et al.  A transition state theory of nonadiabatic unimolecular reactions controlled by a conical intersection. Application to the C2H+4 ion , 1983 .

[18]  M. Pires,et al.  Unimolecular decay paths of electronically excited species. II. The C2H+4 ion , 1978 .

[19]  M. Inghram,et al.  Threshold photoelectron–photoion coincidence mass spectrometric study of ethylene and ethylene‐d4 , 1975 .

[20]  Dudley H. Williams,et al.  Kinetic energy release as a mechanistic probe. Role of orbital symmetry , 1974 .

[21]  R. Marcus Unimolecular dissociations and free radical recombination reactions , 1952 .