Intramolecular Proton Transfer in the Hydrogen Oxalate Anion and the Cooperativity Effects of the Low-Frequency Vibrations: A Driven Molecular Dynamics Study.

We report first-principles molecular dynamics (MD) and dipole-driven molecular dynamics (μ-DMD) simulations of the hydrogen oxalate anion at the MP2/aug-cc-pVDZ level of theory. We examine the role of vibrational coupling between the OH stretching bands, that is, the fundamental and a few combination bands spanning the 2900-3100 cm -1 range, and several of the low-frequency bending and stretching fundamental modes. The low-frequency modes between 300 and 825 cm -1 play a crucial role in the proton-transfer motion. Strong involvement of CO 2 and CCO bending and the CC stretching vibrations indicate that these large amplitude motions cause the shortening of the O···O distance and thus promote H + transfer to the other oxygen by bringing it over the 3.4 kcal/mol barrier. Analysis of resonant μ-DMD trajectories shows that the complex spectral feature near 825 cm -1 , closely corresponding to both an overtone of two quanta of 425 cm -1 and a combination band of low-frequency CO 2 rocking (300 cm -1 ) and CCO bending (575 cm -1 ) modes, is involved in the proton transfer. μ-DMD shows that exciting the system at these mode combinations leads to faster barrier activation than exciting at the OH fundamental mode.