Model trans geometry of the water-dimer system. Depicted are the coupling ( and ) and tuning ( and ) coordinates of the system. Atom labels used throughout this paper are shown.
(solid line) and (dash-dotted line) states in the function of and at two constant distances, with . On picture (a) which is a cut passing through the GM energy geometry. On picture (b) the bond is elongated to to show an intersection of the and states. Plots are cubic splines of points evaluated by the RI-CC2 method.
Diabatic potential surfaces of the (left) and (right) electronic states as functions of , tuning coordinates, with (trans). The isoenergy lines are plotted in the range of [0.0, 8.0] eV with a 0.1 eV step. The black area on the PES represents the CI-seam neighborhood (size exaggerated for purpose of clarity). The “ × ” marks the GM of the and the FC region. GM of the surface is marked as Gl.Min., and the FC region of the surface is marked as FC. The three colored areas show the reaction channels dissociation borders: green for , red for , and yellow for (see Table I for detailed reaction channel description). The dissociation channel numbers are given in dark-green fonts.
Adiabatic PESs in the area of the conical seam. The PESs are plotted as functions of the , coordinates with (trans) [picture (a)]—the CI seam has been marked green (width of seam exaggerated). Double cone of the adiabatic PESs plotted as functions of the and with [picture (b)].
Diabatic (blue dashed lines) and adiabatic (red solid lines) population dynamics excluding time-accumulated flux in the unconstrained water-dimer system for various initial vibrational conditions: label (a), (1,0,0) label (b), (0,2,0) label (c), and (0,0,1) label (d). The dynamics starts with 100% electronic population on the excited state surface.
Time accumulated flux through six diabatic dissociation channels in the unconstrained water-dimer system in various initial vibrational conditions —solid line, (1,0,0)—dashed line, (0,2,0)—dotted line, and (0,0,1)—dashed-dotted line. Subfigures show comparison for separate dissociation channels: the left column presents results for the channels (1), (2), (3), while the right column presents results for the channels , , , respectively. Please note that the probability scale for the left column is more than ten times smaller.
Snapshots of WP probability density averaged over the coupling dimension for the propagation on diabatic state surfaces in the system with initial condition. Upper pictures show the WP on the state surface, lower pictures - on the surface. The scale is automatically set to show maximum amplitude of WP probability density. Pictures (a), (b), (c), and (d) show the WP at 0, 15, 40, and 300 fs, respectively. Note that the grid used for propagation (, coordinate system) has the same size, but is rotated by 45° counterclockwise. For convenience of the reader, the CI area has been marked green.
Diabatic (blue dashed lines) and adiabatic (red solid lines) population dynamics in the constrained water-dimer system for various initial vibrational conditions: label (a), (1,0,0) label (b), (0,2,0) label (c), and (0,0,1) label (d). The dynamics starts with 100% electronic population on the excited state surface.
Reaction channels in the unconstrained water-dimer system in the and states with their expected products and ranges of coordinates. The arbitrary border between channels ( surface) and ( surface) is set to , analogously channels ( surface) and ( surface) are delimited at .
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