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Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions

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Litman,  Yair
Theory, Fritz Haber Institute, Max Planck Society;
Institute for Chemistry and Biochemistry, Freie Universität Berlin;

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Rossi,  Mariana
Theory, Fritz Haber Institute, Max Planck Society;
Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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2005.13314.pdf
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Citation

Litman, Y., & Rossi, M. (in preparation). Multidimensional Hydrogen Tunneling in Supported Molecular Switches: The Role of Surface Interactions.


Cite as: http://hdl.handle.net/21.11116/0000-0006-782E-1
Abstract
The nuclear tunneling crossover temperature (Tc) of hydrogen transfer reactions in supported molecular-switch architectures can lie close to room temperature. This calls for the inclusion of nuclear quantum effects (NQE) in the calculation of reaction rates even at high temperatures. However, standard computations of NQE relying on parametrized dimensionality-reduced models, quickly become inadequate in these environments. In this letter, we study the paradigmatic molecular switch based on porphycene molecules adsorbed on metallic surfaces with full-dimensional calculations that combine density-functional theory for the electrons with the semi-classical ring-polymer instanton approximation for the nuclei. We show that the double intramolecular hydrogen transfer (DHT) rate can be enhanced by orders of magnitude due to surface fluctuations in the deep tunneling regime. We also explain the origin of an Arrhenius temperature-dependence of the rate below Tc and why this dependence differs at different surfaces. We propose a simple model to rationalize the temperature dependence of DHT rates spanning diverse fcc [110] surfaces.