(a) Vibrational energy levels and relaxation channels of monomeric water molecules after OH bend (left-hand side) and OH stretch excitation (right-hand side). (b) Possible IR transitions observable OH bend (left-hand side) and OH stretch excitation (right-hand side); the anharmonic shift of each transition is given in terms of the respective anharmonic constant .
Numerical simulations of excess population on the vibrational modes ⟨100∣, ⟨001∣, ⟨020∣, and ⟨100∣ after ⟨001∣ excitation: (a) , (b) , and (c) . (d) Population difference : positive values representing stimulated emission (for details see text).
Transient spectra of in in the OH bending region, measured after excitation of symmetric OH stretch (circles), antisymmetric OH stretch (squares), and OH bend (triangles); individual curves normalized and vertically shifted for clarity.
Transient spectrum of in in the OH stretching region after excitation of symmetric OH bending mode: squares represent experimental data and vertical lines specify the position of the four Lorentzian lines of the best fit curve (solid curve).
Transient time traces obtained after excitation of the antisymmetric OH stretch for in (left-hand side) [(a) and (b)] and in (right-hand side) [(c) and (d)]. The upper panels [(a) and (c)] refer to experiments with identical pump and probe frequency, the lower ones [(b) and (d)] were measured in the individual maximum of induced absorption. Experimental points and calculated curves; for details see text.
(Upper part) Fundamental frequencies and bandwidths of molecule in gas phase (after Ref. 16) and in the solvents and in liquid phase. (Lower part) Anharmonic constants of molecule, as obtained in this work; values for gas phase (also from Ref. 16) for comparison.
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