TY - JOUR A1 - Wirth, Jonas A1 - Monturet, Serge A1 - Klamroth, Tillmann A1 - Saalfrank, Peter T1 - Adsorption and (photo-) electrochemical splitting of water on rutile ruthenium dioxide JF - epl : a letters journal exploring the frontiers of physics N2 - In this work, the adsorption and splitting of the water molecule by light and/or an external potential is investigated in the frame of (photo-) electrochemical cells using a rutile ruthenium dioxide anode. With the help of periodic density functional calculations, the adsorbed structures of H(2)O and some radicals involved in the splitting process (O, OH, OOH) are obtained and compared with the available experimental results. On the basis of these electronic-structure calculations, we use a method to calculate the stability of the reaction intermediates and conclude on the thermodynamical possibility of the water splitting reaction at the surface. We demonstrate that a moderate overpotential of 0.64 V is required for the reaction to take place at the RuO(2)(110) surface. Y1 - 2011 U6 - https://doi.org/10.1209/0295-5075/93/68001 SN - 0295-5075 VL - 93 IS - 6 PB - EDP Sciences CY - Mulhouse ER - TY - JOUR A1 - Füchsel, Gernot A1 - Klamroth, Tillmann A1 - Monturet, Serge A1 - Saalfrank, Peter T1 - Dissipative dynamics within the electronic friction approach the femtosecond laser desorption of H-2/D-2 from Ru(0001) JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - An electronic friction approach based on Langevin dynamics is used to describe the multidimensional (six-dimensional) dynamics of femtosecond laser induced desorption of H-2 and D-2 from a H(D)-covered Ru(0001) surface. The paper extends previous reduced-dimensional models, using a similar approach. In the present treatment forces and frictional coefficients are calculated from periodic density functional theory (DFT) and essentially parameter-free, while the action of femtosecond laser pulses on the metal surface is treated by using the two-temperature model. Our calculations shed light on the performance and validity of various adiabatic, non-adiabatic, and Arrhenius/Kramers type kinetic models to describe hot-electron mediated photoreactions at metal surfaces. The multidimensional frictional dynamics are able to reproduce and explain known experimental facts, such as strong isotope effects, scaling of properties with laser fluence, and non-equipartitioning of vibrational, rotational, and translational energies of desorbing species. Further, detailed predictions regarding translations are made, and the question for the controllability of photoreactions at surfaces with the help of vibrational preexcitation is addressed. Y1 - 2011 U6 - https://doi.org/10.1039/c0cp02086a SN - 1463-9076 VL - 13 IS - 19 SP - 8659 EP - 8670 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Tremblay, Jean Christophe A1 - Monturet, Serge A1 - Saalfrank, Peter T1 - The Effects of electron-hole pair coupling on the infrared laser-controlled vibrational excitation of NO on Au(111) JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - In this work, we present theoretical simulations of laser-driven vibrational control of NO adsorbed on a gold surface. Our goal is to tailor laser pulses to selectively excite specific modes and vibrational eigenstates, as well as to favor photodesorption of the adsorbed molecule. To this end, various control schemes and algorithms are applied. For adsorbates at metallic surfaces, the creation of electron hole pairs in the substrate is known to play a dominant role in the transfer of energy from the system to the surroundings. These nonadiabatic couplings are included perturbatively in our reduced density matrix simulations using a generalization of the state-resolved position-dependent anharmonic rate model we recently introduced. An extension of the reduced density matrix is also proposed to provide a sound model for photodesorption in dissipative systems. Y1 - 2011 U6 - https://doi.org/10.1021/jp205902k SN - 1089-5639 VL - 115 IS - 39 SP - 10698 EP - 10707 PB - American Chemical Society CY - Washington ER -