Pruning the Hamiltonian Matrix in MULTIMODE: Test for C2H4 and Application to CH3NO2 Using a New Ab Initio Potential Energy Surface.

Abstract

We report vibrational self-consistent field/virtual state configuration interaction energies of nitromethane using the code MULTIMODE and a new full-dimensional potential energy surface (PES). The PES is a precise, permutationally invariant linear least-squares fit to 17,049 electronic energies, using the CCSD(T)-F12b method with HaDZ basis (cc-pVDZ basis for H atoms, and aug-cc-pVDZ basis for C, O, N atoms). Nitromethane has 15 vibrational degrees of freedom, including one that is a nearly free internal methyl torsion, which is accurately described by the PES. This torsional mode makes vibrational calculations very challenging and here we present the results of calculations without it. Nevertheless, 14-mode calculations are still challenging and can lead to very large Hamiltonian matrices. To address this issue, we apply a pruning scheme, suggested previously by Handy and Carter, that reduces the size of matrix without sacrificing accuracy in the eigenvalues. The method is briefly described here in the context of partitioning theory. A new and more efficient implementation of it, coded in the latest version of MULTIMODE program, is described. The accuracy and efficiency are demonstrated for 12-mode C2H4 and then applied to CH3NO2. Agreement with available experimental values of the CH3NO2 14 fundamentals is very good. Diffusion Monte Carlo calculations in full dimensionality are done for the zero-point energy and wavefuction. These indicate that the torisonal motion is nearly a free-rotor in this state.