We present a new approach based on the block-Davidson scheme which provides eigenvalues and eigenvectors of highly excited (ro) vibrational states of polyatomic molecules. The key ingredient is a prediagonalized-perturbative scheme applied to a subspace of a curvilinear normal-mode basis set. This approach is coupled to the Jacobi vector description recently developed by our group [C. Leforestier, A. Viel, F. Gatti, C. Munoz, and C. Iung, J. Chem. Phys. 114, 2099 (2001)], and applied to the HFCO and H2CO molecules, which represent the main difficulties of such calculations for any available method. The first one presents a significant state density because of its low symmetry and the presence of a fluorine atom, while strong resonances and intermode couplings occur in H2CO. This study establishes the robustness, the numerical efficiency, and the versatility of the method which is compared to the regular Lanczos and Davidson schemes. It is also shown that the eigenvectors can be obtained within a given accuracy easily set by the user. This point constitutes one of the main advantages of the method as very few potential-energy surfaces achieve an accuracy of the order of a wave number for highly excited states. Furthermore, this method allows one to restrict the calculations to selected energy levels based on their zero-order descriptions.

We described an improved version of a modified Davidson scheme previously introduced (F. Ribeiro, C. Iung and C. Leforestier, Chem. Phys. Lett.362, 199 (2002)), aimed at computing highly excited energy levels of polyatomic molecules. The key ingredient is a prediagonalization-perturbation step performed on a subspace of a curvilinear normal modes basis set (including diagonal anharmonicities). The efficiency of the method is demonstrated by computing the lowest 350 vibrational states of A′ symmetry of the HFCO molecule. Also shown is the possibility to restrict the calculation to selected energy levels, based on their zero-order description. This State Filtered Diagonalization method is illustrated on a high overtone (7ν5) of the OCF bend, and on the few energy levels (20) which have been experimentally assigned up to 5000 cm -1 of excitation energy.

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We calculated highly excited states of the HFCO molecule, comparing results from two methods. In the first method, Van Vleck perturbation theory is used to transform away all off-diagonal couplings except those between nearly degenerate states. This perturbative transformation leads to a matrix representation where eigenvalues are obtained with relatively small matrices. In the second method, variational eigenvalues are obtained by combining the Jacobi-Wilson approach with the block-Davidson scheme. The key ingredient here is a prediagonalized-perturbative scheme applied to a subspace of a curvilinear normal-mode basis set. Comparisons of the two methods provide a critical test of the less time-consuming perturbation theory. Two different coordinate sets are used to test the sensitivity of the results to coordinate choice. Perturbation theory also requires a polynomial fit to the potential. The implications of this restriction are investigated.