Plot of the model potential energy surface with contours representing 2000 cm−1equipotential lines. The O–O bond is fixed to the equilibrium length. The oxygen atoms are symmetrically placed on the x-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 adiabatic basis of the potential.
The squared amplitude of the |4 0〉0 and |5 0〉0 spectroscopic Hamiltonian ZOB functions in panels (a) and (b), respectively. |4 0〉0 illustrates a “conventional” basis function, while |5 0〉0 illustrates an “unconventional” basis function (see text for the meaning of these terms).
The squared amplitude of |0 9〉0, |0 10〉0, and |0 11〉0 spectroscopic Hamiltonian ZOB functions, in panels (a)-(c), respectively. The first illustrates a “conventional” basis function, the second is between “conventional” and “unconventional,” and the last illustrates an “unconventional” basis function.
Two snapshots of the time evolution of the squared amplitude of the |5 0〉0 spectroscopic ZOB function as propagated on the potential surface. These snapshots are at t = 0.765 ps and t = 0.830 ps for panels (a) and (b), respectively. These plots show that although the ZOB at t = 0 appears unconventional, in truth it contains a linear combination of a conventional form and a form understandable in terms of a “horseshoe” shape periodic orbit.
The squared amplitude of the ZOB for the 2:1, N = 9 polyad, starting at the top with |4 1〉0 and proceeding downward through |3 3〉0 , |2 5〉0, |1 7〉0, and |0 9〉0. The left hand column displays the ZOB at time zero, while the right hand column shows the ZOB at a specific time that highlights the “conventional” nature of the basis function.
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