REMPI-TOF studies of the translational anisotropy and the polarization of the O ((1)D2) photofragment angular momentum following ozone photolysis at 298 nm.
The translational anisotropy and the polarization of the electronic angular momentum of the O ((1)D2) fragment produced from the 298 nm photodissociation of ozone have been determined using resonance enhanced multiphoton ionization (REMPI) in conjunction with time-of-flight mass spectrometry (TOFMS). The translational anisotropy parameter beta, which is necessarily averaged over the O2 co-fragment rotational distribution, is measured to be 1.08 +/- 0.04. This is consistent with that expected for the (1)B2 <-- (1)A1 transition within an impulsive model if the tangential velocity associated with the zero point motion of the bend is constricted to opening the bond angle. Molecular frame polarization parameters of rank up to k = 4 have been extracted for the O ((1)D2) fragment and the calculated m(J) populations show a strong preference for the absolute value(m(J)) = 1 states. A small coherence term is also observed, a manifestation of the nuclear geometry of the dissociating molecule and the existence of possible non-adiabatic processes in the exit channel. The orientation associated with the mapping of the photon helicity onto the O ((1)D2) electronic angular momentum distribution was observed to have been quenched. However, the parameter gamma1', which describes the contribution to the orientation from a coherent superposition of a parallel and perpendicular excitation where the photofragment angular momentum lies perpendicular to both the recoil velocity and to the transition dipole moment, was determined to be -0.06.
Denzer
W
W
Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, UK OX1 3QZ.
Horrocks
S J
SJ
Pearson
P J
PJ
Ritchie
G A D
GA
D016880:Anisotropy; D017666:Deuterium Oxide / Q000737:chemistry*; D008432:Mathematical Computing; D010100:Oxygen / Q000737:chemistry*; D010126:Ozone / Q000737:chemistry*; D010777:Photochemistry; D010782:Photolysis; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods
D010126:Ozone; D017666:Deuterium Oxide; D010100:Oxygen