Bending dissociation

T. Suzuki, S. Nanbu, Non-adiabatic bending dissociation of OCS induced by orbital unlocking, Low-Lying Potential Energy Surfaces, ACS Symposium Series 828 (2002) 300-313. 

Non-Adiabatic Bending Dissociation of OCS Induced by Orbital Unlocking... 

Variational RRKM theory is particularly important for imimolecular dissociation reactions, in which vibrational modes of the reactant molecule become translations and rotations in the products [22]. For CH —> CHg+H dissociation there are tlnee vibrational modes of this type, i.e. the C—H stretch which is the reaction coordinate and the two degenerate H—CH bends, which first transfomi from high-frequency to low-frequency vibrations and then hindered rotors as the H—C bond ruptures. These latter two degrees of freedom are called transitional modes [24,25]. C2Hg 2CH3 dissociation has five transitional modes, i.e. two pairs of degenerate CH rocking/rotational motions and the CH torsion. 

The influence of intermolecular bending excitation of the Ne IC1(B, v = 2) complex [97] and of intermolecular bending and rotational excitation of the Ne Cl2(fi, v = 11) complex [112] has been considered theoretically. To date, however, there are no complimentary experimental results reported to complement the predictions. The observation of the linear features in the excitation spectra of Rg XY complexes enables dynamics to be investigated over broader regions of the excited state PES. Thus far, we have investigated the VP of He I C1(B, v = 2, 3) dissociation with n >2 [51]. 

H2S adsorption on the (2x2)-S covered Pt(lll) surface at IlOK contrasts with adsorption on the clean surface. On the (2x2)-S surface no complete dissociation Is observed at low temperature Instead, H2S partially dissociates to form an adsorbed SH Intermediate with a characteristic bend vibration at 585 cm . Heating adsorbed SH on the (2x2)-S covered surface leads to a SH+H recombination reaction not observed on clean Ft. The recombination process removes the excess SH so that the stable, high coverage (/3 X /3)R30 -S lattice can be formed. 

Therefore, we arrive at the same conclusion for the mechanism of COad oxidation in the lower potential regime as for Pt-free Ru(OOOl), postulating that at potentials E < 0.55 V, only strongly bound OHad/Oad species are present in the mixed COad + OHad/Oad adlayer, which are not reactive towards CO2 formation, while for E > 0.55 V, additional, weakly adsorbed OHad/Oad species are formed, which can react with the (likewise destabilized) COad- Similar to COad oxidation on a Ru(OOOl) surface, the reaction starts by dissociative adsorption of H2O on the Ru(OOOl) surface (no shift in the onset potential). In this case, however, the Pt islands can accelerate the reaction by accepting the Hupd resulting from a homolytic dissociation process. Thus, we tentatively propose a mechanism for CO oxidation at potentials between the reaction onset up to the bending point (see also Lin et al. [1999]), which is... 

For the same reason, Ru(OOOl) modihcation by Pt monolayer islands results in a pronounced promotion of the CO oxidation reaction at potentials above 0.55 V, which on unmodified Ru(OOOl) electrodes proceeds only with very low reaction rates. The onset potential for the CO oxidation reaction, however, is not measurably affected by the presence of the Pt islands, indicating that they do not modify the inherent reactivity of the O/OH adlayer on the Ru sites adjacent to the Pt islands. At potentials between the onset potential and a bending point in the j-E curves, COad oxidation proceeds mainly by dissociative H2O formation/ OHad formation at the interface between the Ru(OOOl) substrate and Pt islands, and subsequent reaction between OHad and COad- The Pt islands promote homo-lytic H2O dissociation, and thus accelerate the reaction. At potentials anodic of the bending point, where the current increases steeply, H2O adsorption/OHad formation and COad oxidation are proposed to proceed on the Pt monolayer islands. The lower onset potential for CO oxidation in the presence of second-layer Pt islands compared with monolayer island-modified Ru(OOOl) is assigned to the stronger bonding of a double-layer Pt film (more facile OHad formation). 

It is unclear exactly how the two potential surfaces, and hence the interaction regions between them, behave as the parent molecules bend. Our experimental results indicate that the more bent the ozone molecules are as they dissociate the more effectively is the available energy channelled into the OA T, ) fragment vibration. It is possible that as the parent molecules bend, the crossing seams move to a region on the repulsive state that more strongly favors the production of vibrationally excited 02(3 ) fragments. 

Figure A.17 Most likely dissociation path of CO on Rh(lll). In the transition state, CO bends across a rhodium atom, which gives optimum overlap between Rh d and CO 2p orbitals (from deKoster etal. [211).

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