Using collocation and a hierarchical basis to solve the vibrational Schrödinger equation.

We show that it is possible to compute vibrational energy levels of polyatomic molecules with a collocation method and a basis of products of one-dimensional harmonic oscillator functions pruned so that it does not include functions for which the indices of many of the one-dimensional functions are nonzero. Functions with many nonzero indices are coupled only by terms that depend simultaneously on many coordinates, and they are typically small. The collocation equation is derived without invoking differences of interpolation operators, which simplifies implementation of the method. This, however, requires inverting a matrix whose elements are values of the pruned basis functions at the collocation points. The collocation points are the points on a Smolyak grid whose size is equal to the size of the pruned basis set. The Smolyak grid is built from symmetrized Leja points. Because both the basis and the grid are not tensor products, the inverse is not straightforward. It can be done by using so-called hierarchical 1-D basis functions. They are defined so that the matrix whose elements are the 1-D hierarchical basis functions evaluated at points is lower triangular. We test the method by applying it to compute 100 energy levels of CH2NH with an iterative eigensolver.

Ro-vibronic transition intensities for triatomic molecules from the exact kinetic energy operator; electronic spectrum for the C̃ 1B2 ← X̃ 1A1 transition in SO2.

A procedure for calculating ro-vibronic transition intensities for triatomic molecules within the Born-Oppenheimer approximation is reported. Ro-vibrational energy levels and wavefunctions are obtained with the DVR3D suite, which solves the nuclear motion problem with an exact kinetic energy operator. Absolute transition intensities are calculated both with the Franck-Condon approximation and with a full transition dipole moment surface. The theoretical scheme is tested on C̃ 1B2 ← X̃ 1A1 ro-vibronic transitions of SO2. Ab initio potential energy and dipole moment surfaces are generated for this purpose. The calculated ro-vibronic transition intensities and cross sections are compared with the available experimental and theoretical data.

Simulating electric field interactions with polar molecules using spectroscopic databases.

Ro-vibrational Stark-associated phenomena of small polyatomic molecules are modelled using extensive spectroscopic data generated as part of the ExoMol project. The external field Hamiltonian is built from the computed ro-vibrational line list of the molecule in question. The Hamiltonian we propose is general and suitable for any polar molecule in the presence of an electric field. By exploiting precomputed data, the often prohibitively expensive computations associated with high accuracy simulations of molecule-field interactions are avoided. Applications to strong terahertz field-induced ro-vibrational dynamics of PH3 and NH3, and spontaneous emission data for optoelectrical Sisyphus cooling of H2CO and CH3Cl are discussed.