Photodetachment of probes the transition state region. The ground state vibrational wave function for (shaded region) is superimposed on a model collinear potential energy surface for the reaction. The saddle point on the reactive surface is marked with an X (from Ref. 8).
Solid lines are experimental photoelectron spectra of para- (left) and (right). Dashed lines are exact simulations using anion surface from Ref. 66 and surface from Ref. 67. The peaks around are progressions in internal rotor states, while the smaller peaks around involve stretch excitation (adapted from Ref. 69).
(Color) Bottom: Reaction coordinates for and reactions, showing calculated energetics of the and minima. Top: Contour plots for anion vibrational wave function in ground (red) and second excited state (blue) (from Ref. 82).
(Color) Photoelectron spectra of at laser polarization angles (top) and 90° (bottom). Experimental and simulated spectra are shown as red and black lines, respectively (from Ref. 82).
Potential energy curves for and the , , and states of ArCl (From Ref. 101).
Experimental and ZEKE spectra of . Peaks 1, 2, and 3 are vibrational origins of transitions to the neutral , , and states (from Ref. 101).
Schematic of fast radical beam photodissociation experiment with photofragment coincidence detection scheme (from Refs. 138 and 140).
Photofragment yield spectrum for radical (from Ref. 159).
Photofragment translational energy distributions for fragments from photodissociation of at several excitation energies. Clear vibrational progressions in the umbrella mode are seen (from Ref. 159).
Relevant stationary points on the ground state potential energy surface (from Ref. 140).
Photofragment translation energy distributions and anisotropy parameters for and channels from photodissociation of (from Ref. 140).
Schematic of three-pulse femtosecond stimulated emission pumping (FSEP) experiment with photoelectron detection. The potential energy curves shown correspond to the and states of and the state of (from Ref. 191).
Observation of coherences in FSEP experiment. Curves show integrated signals at high electron kinetic energy for bare and clustered as a function of time at two excitation energies (from Ref. 191).
(a) Electronic level energetics of are characterized by a bound -like ground state and three nearly degenerate bound -like excited states below the vertical binding energy (VBE). Pump-probe photodetachment images/spectra have contributions from (A) above-VBE detachment at the probe laser energy; (B) above adiabatic binding energy (ABE) photodetachment at the pump laser energy; (C) resonant two-photon detachment (R2PD) at the pump energy; and (D) resonant, time-dependent, two-color, two-photon pump-probe detachment signal. (b) Spectral waterfall plots of time-resolved photoelectron spectra of (isomer I) (from Ref. 195).
Size-, isotopomer-, and isomer-dependent excited state electronic lifetime trends of water cluster anions. Lifetimes are plotted against . Bulk lifetimes were taken from Ref. 204. Dotted lines, added to guide the eye, demonstrate the linear extrapolation of cluster excited state lifetimes to the bulk for (from Ref. 195).
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