Arnoldi Algorithm for the Simulation of Multidimensional Infrared Spectroscopy

Abstract

The cubic and quartic anharmonic force field of malonaldehyde is calculated using density functional theory at the B3LYP/6-31G(d,p) level, and used to simulate coherent infrared vibrational spectra. 12 normal modes are included in the simulation, and the Arnoldi method is employed for the diagonalization of the Hamiltonian. The calculated three pulse infrared signals in the k1 + k2 - k3 direction show signatures of the intramolecular hydrogen bond couplings between the C=O stretch, H-O-C bend and O-H stretch vibrations.