engleski

Multidimensional Quantum Dynamics of Carboxylic Acid Dimers

Due to their prototype character, carboxylic acid dimers have been in the focus of experimental and theoretical studies for decades. From the theoretical point of view, the quantum nature of the hydrogen and the strong coupling between its motion and that of the molecular framework lead to multidimensional quantum dynamics. Here various aspects of the theoretical simulation of vibratonal and vibrational-rotational-tunneling spectra will be discussed. First, on the specific example of formic and acetic acid dimmers we will show how the broad stationary absorption OH-stretching bands can be understood in terms of multiple conformers and multidimensional anharmonic vibrational dynamics [1, 2]. Next, the focus will be on the hydrogen tunneling motion. The recently developed general approximation to the reaction path (GARP) method will be presented and applied it to the description of the double proton transfer reaction in the formic acid dimer isotopologues [3, 4]. We will address questions such as: Does vibrational excitation promotes H-tunneling? Which molecular motions are important for the understanding tunneling motion in the formic acid dimer? Does isotope substitution affect the mechanism of H-transfer.

hydrogen bonds ; multidimensional quantum dynamics

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