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Abstract:

Many classes of organic reactions exhibit a remarkable increase in reaction rates when they occur at the water–organic interface. Although this observed ‘on-water’ catalysis has been extensively studied, the suggested mechanisms still do not explain some of the experimental findings. The mechanism proposed by Jung and Marcus (JACS 129, 5492 (2007)) involves stabilising the transition-state (TS) complex via H-bonds to ‘dangling’ interfacial water molecules. Although the reactants also experience H-bonding to interfacial water molecules in the reactant configuration, it has been argued that the H-bonds are enhanced, in terms of number and strength, in the TS. Therefore, the observed decrease in activation energy has been attributed to this preferential enhancement of H-bonds which leads to a more pronounced TS stabilisation. We employ energy decomposition analysis using the method of absolutely localised molecular orbitals to study this proposition. We find that H-bonds to interfacial water molecules are equivalent in the TS and reactant configurations. Nevertheless, these H-bonds result in significantly enhanced charge-transfer between the reactants in the TS complex, which rationalises the decrease in activation energy.

Bio:

Thomas D. Kühne, studied computer science (B. Sc. ETH in 2003) and computational science and engineering (Dipl.-Rech. Wiss. ETH in 2005) with a focus in theoretical chemistry at ETH Zürich. Thereafter, he worked under the mentorship of Prof. Michele Parrinello in Lugano, where he obtained his Doctor of Science degree in theoretical physics in 2008 also from ETH Zürich. After postdoctoral research on multiscale simulation methods within the theoretical condensed matter group at Harvard University, he joined the University of Mainz as an assistant professor in theoretical chemistry in 2010. In 2014 he then moved to Paderborn, as a tenured associate professor in „Theoretical Interface Chemistry“, where he was promoted to full professor in 2018 and now holds the newly established Chair of Theoretical Chemistry.