Direct mapping of recoil in the ion-pair dissociation of molecular oxygen by a femtosecond depletion method.
Time-resolved dynamics of the photodissociation of molecular oxygen, O(2), via the (3)Sigma(u) (-) ion-pair state have been studied with femtosecond time resolution using a pump-probe scheme in combination with velocity map imaging of the resulting O(+) and O(-) ions. The fourth harmonic of a femtosecond titanium-sapphire (Ti:sapphire) laser (lambda approximately 205 nm) was found to cause three-photon pumping of O(2) to a level at 18.1 eV. The parallel character of the observed O(+) and O(-) images allowed us to conclude that dissociation takes place on the (3)Sigma(u) (-) ion-pair state. The 815 nm fundamental of the Ti:sapphire laser used as probe was found to cause two-photon electron photodetachment starting from the O(2) ion-pair state, giving rise to (O((3)P)+O(+)((4)S)) products. This was revealed by the observed depletion of the yield of the O(-) anion and the appearance of a new O(+) cation signal with a kinetic energy E(transl)(O(+)) dependent on the time delay between the pump and probe lasers. This time-delay dependence of the dissociation dynamics on the ion-pair state has also been simulated, and the experimental and simulated results coincide very well over the experimental delay-time interval from about 130 fs to 20 ps where two- or one-photon photodetachment takes place, corresponding to a change in the R(O(+),O(-)) interatomic distance from 12 to about 900 A. This is one of the first implementations of a depletion scheme in femtosecond pump-probe experiments which could prove to be quite versatile and applicable to many femtosecond time-scale experiments.
Baklanov
Alexey V
AV
Institute of Chemical Kinetics and Combustion, Institutskaja St. 3, Novosibirsk 630090, Russia and Novosibirsk State University, Pirogova St. 2, Novosibirsk 630090, Russia.
Janssen
Liesbeth M C
LM
Parker
David H
DH
Poisson
Lionel
L
Soep
Benoit
B
Mestdagh
Jean-Michel
JM
Gobert
Olivier
O
D003116:Color; D010100:Oxygen / Q000737:chemistry*; D010782:Photolysis; D017785:Photons; D013997:Time Factors
D010100:Oxygen