Vibrational Dynamics of H5 + and Its Deuterated Isotopomers
The vibrational dynamics of the H5 + complex and its deuterated isotopomers H4 D+ , H3 D2 + , H2 D3 + , HD4 + , and D5 + are investigated using a model Hamiltonian which is based on the assumption that on the potential energy hypersurface the barriers for the internal rotation motions are infinitely high except for the practically free propeller-like motion. According to our previous studies on H5 + , the propeller-like rotation essentially does not interact with the remaining vibrations and is therefore neglected in the present calculations. Within the framework of the adiabatic approximation the resulting eight-dimensional vibrational problem is separated into two smaller subproblems which are solved numerically applying the same scheme as previously. The calculations are performed using a new extended potential energy function which also provides a reliable description of the interactions between the degenerate stretching motions and the remaining vibrations. As in our previous calculations, the high-frequency fundamentals obtained for H5 + are in good agreement with their experimental counterparts, whereas the reliability of the present results for the low-frequency motions is considerably improved as a result of the appropriate description of the relevant interactions. Predictions of the vibrational energies of the other deuterated isotopomers are made on the same accuracy level. The zero-point energies derived from the present calculations are believed to be accurate enough for a quantitative determination of the binding energies of the different isotopomers.
spirko
V
J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejskova 3, Prague 8, 182 2, Czech Republic
Kraemer
WP
Soldan
P