Schematic diagram of the photodetachment-photoionization apparatus.
Potential energy curves, plotted as functions of the Cu–O distance , along with laser pump-probe schemes. The dashed curves represent cuts in the hydrogen-bonded orientation, while the solid curves represent the orientation in which the copper atom is closest to the oxygen atom. The vertical arrows represent various pump-probe processes employed in the experiments reported here.
Minimum energy structures of complexes for the three charge states of Cu, where (a) shows the structure of the anion, (b) the neutral, and (c) the cation.
Experimental and calculated photoelectron spectra. The experimental spectrum is shown as black points. The calculated spectrum is reported with a solid, black curve. For comparison we also calculated the photoelectron spectrum after shifting the potential energy curve for by along the Cu–O distance coordinate . The results of these calculations are plotted with gray curves; the dashed line represents the calculation when the potential minimum is shifted to and the dash-dot line represents the results when the minimum is at .
(Color online) Initial experimental time dependence of cation signals. The signal rise from (gray triangles) is fitted with a tanh function (solid line) and used as an in situ measure of the instrument time resolution. The open circles represent signal from , while the filled circles represent the signal from .
(Color online) Experimental time dependence of cation signals resulting from photodetachment-photoionization of . The rising signal (open circles) results from photodetachment followed by two-color resonant ionization. The decaying signal (filled circles) results from photodetachment followed by one-color resonant multiphoton ionization. The solid lines represent the exponential fits to the data used to extract time components.
(Color online) Cuts through the potential energy surfaces along the Cu–O distance coordinate for (i) , (ii) with other coordinates frozen at the anion configuration, and (iii) fully relaxed . The insets show the various solvent orientations for the three minima.
Cuts through the potential energy surfaces along the Cu–O distance coordinate for (i) the anion and (ii) the neutral at the vertical detachment geometries of and . The solid curves represent , while the dashed curves represent . The vertical line is drawn at the Cu–O distance corresponding to the minimum energy configuration of both anions. The horizontal line at indicates the dissociation energy of the neutral complexes.
Select geometrical parameters of all species, calculated at the MP2 level of theory.
Calculated fundamental frequencies of the four vibrational modes corresponding to the one-dimensional (1D) potential energy slices for and , which is the neutral complex in the anion configuration, i.e. the vertical detachment geometry.
Calculated fundamental frequencies for the three vibrational modes corresponding to the 1D potential energy slices of , minimum energy neutral configuration.
Parameters of double exponential fit to the functions given in Eqs. (4) and (5); the indicated errors are of the least squares fit parameters.
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