The predissociation dynamics of H2+XUV→H2 (*)→H(1s)+H(2s,2p) has been studied by measuring the fragment branching ratios between the H(2s) and H(2p) states and the fragment angular distributions using the XUV (extreme ultraviolet) laser pump and UV(ultraviolet) laser probe method. The fragment angular distributions for the predissociation of the 3pπD(1)Πu (+)υ=3 state show parallel transitions, demonstrating that the main components of the dissociating state have (1)Σu (+) symmetry. The measured fragment branching ratios, H(2s)/(H(2s) + H(2p)), for the transitions R(0), R(1), and P(2) in 3pπD(1)Πu (+)υ=3←X(1)Σg (+)υ(″)=0 are in good agreement with one of the previous theoretical predictions. The predissociations of the 3pπD(1)Πu (-)(υ=3) state arising from the Q(1), Q(2), and Q(3) lines have also been observed. The angular distributions and the state distributions of the excited fragments (all found from the H(2p) state) illustrate that the dissociating states for the Q lines have the expected Πu (-) symmetry. The predissociation dynamics of the transition 4pσB(″1)Σu (+)υ=1←X(1)Σg (+)υ(″)=0 was also studied. Their fragment angular distributions show the expected parallel transitions, and most of the fragments are in the H(2s) states. The Beutler-Fano profiles and the associated spectroscopic parameters for the predissociations have also been obtained by measuring the fragment yield of H(2s, 2p) as a function of excitation photon energies.
The photodissociation dynamics of O2, O2 + hυ → O((3)P) + O(2p(3)((4)S)3s, (3)S/(5)S), has been studied by combining the XUV laser pump / UV laser probe and velocity map imaging methods in the photon energy range 14.64-15.20 eV. The fragment yield spectra of O((3)S) and O((5)S) and their velocity map images have been recorded using the state-selective (1+1) REMPI method to detect the fragments. The fragment yield spectra show resolved fine structure that arises from the predissociated Rydberg states I, I' and I″ ((3)Π(Ω = 0,1,2)). The branching ratios between the two decay channels have been measured by one-photon ionization of the fragments O((3)S) and O((5)S) simultaneously. It is surprising to find that the dissociation cross sections for the production of O((5)S) are larger than, or comparable to, those of O((3)S) for the I and I' states, while the cross sections for the production of O((5)S) are smaller than those of O((3)S) for the I″ state. All fragments O((5)S) arise from perpendicular transitions, which provides direct experimental evidence about the symmetry assignments of the states I, I' and I″ excited in this energy region. Although most of the fragments O((3)S) arise from perpendicular transitions, some of them are from parallel transitions. Based on the calculated ab initio potential energy curves, we propose that the neutral dissociation into O((3)P) + O((3)S) occurs mainly via the interaction of the Rydberg states I, I', and I″ with the vibrational continuum of the diabatic 8(3)Π(u) state (1π(u)⁻¹(a⁴Π(u))3sσ(g), ³Π(u)), while the neutral dissociation into O((3)P) + O((5)S) occurs mainly via the interaction of Rydberg states I, I', and I″ with the diabatic 7(3)Π(u) (1π(g)⁻¹(X²Π(g))3pσ(u), ³Π(u)).
The predissociation mechanism of D near the threshold for the production of the D(2s, 2p) fragments has been studied by measuring the fragment yield spectra, fragment velocity map images, and fragment branching ratios D(2s)/(D(2s) + D(2p)) using a combination of XUV laser and velocity map imaging. The predissociation dynamics of the 2pπCΠ(υ = 19) and 3pπDΠ(υ = 4,5) states were studied. The 2pπCΠ(υ = 19) state is a bound state due to a shallow barrier. For the R(0) transition to the 2pπCΠ(υ = 19) state, the experimental results suggest that the predissociation occurs via three channels with decreasing importance: l-uncoupling with the 2pσBΣ state, tunneling, and l-uncoupling with the 3pσB'Σ state. For the R(1) transition to the 2pπCΠ(υ = 19) state, the first channel plays the dominant role. For the Q(1) transition to the 2pπCΠ(υ = 19) state, the predissociation occurs via tunneling as required by symmetry. For the predissociation of the 3pπDΠ(υ = 4,5) states, the experimental data confirm the earlier results indicating that the main perturbing state is 3pσB'Σ. The Beutler-Fano profiles and the associated spectroscopic parameters for the various predissociations have also been obtained. The measured Fano-parameters q for the P- and R-branches of the 3pπDΠ state are found to have opposite signs, and their relationships are in agreement with a formula derived from the Fano equation. Rotationally resolved Beutler-Fano profiles were measured for the P(2) and P(3) lines.
The direct photodissociation of D_{2} at excitation energies above 14.76 eV occurs via two channels, D(2s)+D(1s) and D(2p)+D(1s). The branching ratios between the two have been measured from the dissociation threshold to 3200 cm^{-1} above it, and it is found that they show cosine oscillations as a function of the fragment wave vector magnitudes. The oscillation is due to an interference effect and can be simulated using the phase difference between the wave functions of the two channels, analogous to Young's double-slit experiment. By fitting the measured branching ratios, we have determined the depths and widths of the effective spherical potential wells related to the two channels, which are in agreement with the effective depths and widths of the ab initio interaction potentials. The results of this Letter illustrate the importance of the relative phase between the fragments in controlling the branching ratios of the photodissociation channels.
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