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 CO2 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 CO2 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.

Analysis of the Proton Transfer Bands in the Infrared Spectra of Linear N2H+···OC and N2D+···OC Complexes Using Electric Field-Driven Classical Trajectories.

In this work, we describe ab initio calculations and assignment of infrared (IR) spectra of hydrogen-bonded ion-molecular complexes that involve a fluxional proton: the linear N2H+···OC and N2D+···OC complexes. Given the challenges of describing fluxional proton dynamics and especially its IR activity, we use electric field-driven classical trajectories, i.e., the driven molecular dynamics (DMD) method that was developed by us in recent years and for similar applications, in conjunction with high-level electronic structure theory. Namely, we present a modified and a numerically efficient implementation of DMD specifically for direct (or "on the fly") calculations, which we carry out at the MP2-F12/AVDZ level of theory for the potential energy surface (PES) and MP2/AVDZ for the dipole moment surfaces (DMSs). Detailed analysis of the PES, DMS, and the time-dependence of the first derivative of the DMS, referred to as the driving force, for the highly fluxional vibrations involving H+/D+ revealed that the strongly non-harmonic PES and non-linear DMS yield remarkably complex vibrational spectra. Interestingly, the classical trajectories reveal a doublet in the proton transfer part of the spectrum with the two peaks at 1800 and 1980 cm-1. We find that their shared intensity is due to a Fermi-like resonance interaction, within the classical limit, of the H+ parallel stretch fundamental and an H+ perpendicular bending overtone. This doublet is also observed in the deuterated species at 1360 and 1460 cm-1.

Assignment of Infrared-Active Combination Bands in the Vibrational Spectra of Protonated Molecular Clusters Using Driven Classical Trajectories: Application to N4H+ and N4D.

We investigate the utility of the driven molecular dynamics (DMD) approach to complex molecular vibrations by applying it to linear clusters with several degenerate vibrational modes and infrared (IR) intense combination bands. Here, the prominent features in N4H+ and N4D+ IR spectra, reported and described by others previously, have been characterized for the first time by DMD using recently published high-level potential and dipole moment surfaces. Namely, the calculations closely correlate the parallel proton stretch vibration in N4H+, at 750 cm-1, with the one observed experimentally at 743 cm-1. Second, the intense IR-active combination bands found in experimental spectra within 900-1100 cm-1 have been properly recovered by DMD at 950 cm-1 as strongly IR-active and confirmed as consisting of H+ asymmetric stretch and N2···N2 intermolecular symmetric stretch modes. Furthermore, we show that certain combination bands involving overtone transitions may be recovered by DMD using a hard-driving regime, such as the 1409 cm-1 band measured in N4H+, revealed by DMD at 1375 cm-1, and assigned to a progressive combination of the parallel H+ stretch and two quanta of N2···N2 stretch, in agreement with quantum mechanical studies reported previously by others.