Photoinitiated Reactions in Weakly Bonded Complexes

Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

“…Several spectroscopic techniques have been developed to obtain more direct information about the structure and dynamics at the TS, giving rise to the so called Transition State Spectroscopy (TSS) [5][6][7]. Recently,the development of ultrafast lasers also allows probing of the dynamics in real time [8,9], and if the pulse is properly designed it may be used to control the outcome of the reaction [10,11].…”

“…Recently,the development of ultrafast lasers also allows probing of the dynamics in real time [8,9], and if the pulse is properly designed it may be used to control the outcome of the reaction [10,11]. Moreover, some promising new directions in the field of TSS fill the gap between gas and condensed phases, through the study of solvation effects in mass selected clusters [7,[12][13][14] or heterogeneous chemistry on metal surfaces [15].…”

“…In these spectroscopic studies, the TS is reached via photon excitation from a specific precursor, usually a van der Waals complex between the two reactants [7,[16][17][18][19][20][21][22][23][24][25][26][27] or a stable negative ion [6,[28][29][30][31][32][33]. Using van der Waals complexes as precursors, one alternative developed by Wittig and coworkers [7,26,27] consists in photodissociating one of the reactants ejecting one fragment towards the second partner at restricted geometry conditions, imposed by the structure of the initial van der Waals precursor. In a second possibility, one of the partners within the complex is promoted to excited electronic states where the reaction takes place, as first done by Soep and co-workers [16][17][18][19][20], and lately applied by Polanyi and co-workers [21][22][23] and González-Ureña and co-workers [24,25].…”