Quantum dynamics with sparse grids: A combination of Smolyak scheme and cubature. Application to methanol in full dimensionality

Quantum dynamical approaches based on product-grids are limited to the studies of molecular systems with few degrees of freedom, typically less than ten. Recently, Avila et al. [G. Avila, T. Carrington, J. Chem. Phys., 131 (2009) 1741031 have introduced the Smolyak scheme [S.A. Smolyak, Soy. Math. Dokl., 4 (1963) 2401, which considerably reduces the size of the grids. This approach has pushed back the present calculation limits on the vibrational spectra of polyatomic molecules. In the present study, we have developed an extension of the standard Smolyak scheme in which this scheme is combined with multidimensional grids, such as cubatures, to obtain new sparse grids. This scheme has been applied to the study of the torsional energy levels of methanol in full dimensionality (12D). (C) 2013 Elsevier B.V. All rights reserved.