In this article we review state-of-the-art methods for computing vi-brational energies of polyatomic molecules using quantum mechanical, variationally-based approaches. We illustrate the power of those methods by presenting applications to molecules with more than four atoms. This demonstrates the great progress that has been made in this field in the last… (More)
Anharmonic vibrational spectroscopy calculations using MP2 and B3LYP computed potential surfaces are carried out for a series of molecules, and frequencies and intensities are compared with those from experiment. The vibrational self-consistent field with second-order perturbation correction (VSCF-PT2) is used in computing the spectra. The test calculations… (More)
In this paper we propose a new quadrature scheme for computing vibrational spectra and apply it, using a Lanczos algorithm, to CH(3)CN. All 12 coordinates are treated explicitly. We need only 157'419'523 quadrature points. It would not be possible to use a product Gauss grid because 33 853 318 889 472 product Gauss points would be required. The nonproduct… (More)
We demonstrate that the combination of simply contracted basis functions and the Lanczos algorithm yields an extremely efficient method for computing vibrational energy levels. In this paper we discuss the ideas, and present some results for CH4. The basis functions we use are products of eigenfunctions of reduced-dimension Hamiltonians obtained by freezing… (More)
a r t i c l e i n f o a b s t r a c t A new criterion for choosing the time step used when numerically solving time-dependent Schroedinger equation with the Lanczos method is presented. Following Saad, Stewart and Leyk, an explicit expression for the time step is obtained from the remainder of the Chebyshev series of the matrix exponential.