Plot of the model two-dimensional potential energy surface for HO2 with contours representing 2000 cm−1 equipotential lines. The O–O bond is fixed to the equilibrium length. The oxygen atoms are symmetrically placed on the XH axis about zero.
The effective bend potentials for OH stretching states n s = 0–5. Obtaining the symmetric bending wavefunctions from these potentials yields the final adiabatic ZOB.
An example of an adiabatic ZOB state that is later used as an initial wavepacket for time propagation on the potential surface. This state corresponds to |4 1〉0.
Comparison of the time evolution between the potential surface (black trace) and the best frequency domain effective Hamiltonians (, red trace). Panels (a)–(d) correspond to P(t) for |4 0〉0, |4 1〉0, |5 0〉0, and |5 1〉0, respectively. The effective Hamiltonian yields different dynamics and quickly falls out of phase.
The short time behavior of |5 1〉0 for three different effective Hamiltonians compared to that of the potential surface. See text for a detailed description.
Comparison of the time evolution between the potential surface (black trace) and the ultrafast effective Hamiltonian, (red trace). Panels (a)–(d) correspond to P(t) for |4 0〉0, |4 1〉0, |5 0〉0, and |5 1〉0, respectively. Significantly better agreement between the potential and the effective Hamiltonian is now obtained as compared to Figs. 4 and 5.
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