Multidimensional infrared signatures of intramolecular hydrogen bonding in malonaldehyde

The sixth-order anharmonic force field of malonaldehyde along the two proton-transfer double-well coordinates and the four O-H and C=O stretching modes is constructed at the MP2/6-31G(d,p) level. The vibrational Hamiltonian is diagonalized using the Arnoldi method. Coherent infrared (IR) vibrational spectra are predicted using the vibrational eigenstates. The three pulse IR signals, calculated in all possible phase matching directions, show specific signatures of the intramolecular proton transfer.