Six-dimensional vibrational analysis of coupled intermolecular vibrations in a binary cluster.
We report on full- (six-) dimensional calculations of the intermolecular vibrations of a binary aromatic-solvent cluster. An exact Hamiltonian for this kind of interaction is modified in a general manner in order to perform calculations of molecules without symmetry. The binary cluster phenol(H2O)1 is used as a test case since its intermolecular vibrations are anharmonic and highly coupled. The formulation of the Schrodinger equation leads to a complex-valued eigenvalue problem with a dimension larger than two million, which is solved by filter diagonalization to obtain both eigenvalues and eigenvectors. With the knowledge of the eigenvectors, an interpretation of all eigenvalues is possible by a characterization with pseudoquantum numbers that are related to the widely used nomenclature of intermolecular normal motions in aromatic(solvent) clusters.
Jansen
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Heinrich-Heine-Universitat Dusseldorf, Institut fur Physikalische Chemie I, Universitatsstrasse 26.33.O2, 40225 Dusseldorf, Germany.
Gerhards
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