Wavepacket dynamical study of H-atom tunneling in catecholate monoanion: the role of intermode couplings and energy flow.

We present a study of H-atom tunneling in catecholate monoanion through wavepacket dynamical simulations. In our earlier study of this symmetrical double-well system [Phys. Chem. Chem. Phys., 2022, 24, 10887], a limited number of transition state modes were identified as being important for the tunneling process. These include the imaginary frequency mode Q1, the CO scissor mode Q10, and the OHO bending mode Q29. In this work, starting from non-stationary initial states prepared with excitations in these modes, we have carried out wavepacket dynamics in two and three dimensional spaces. We analyse the dynamical effects of the intermode couplings, in particular the role of energy flow between the studied modes on H-atom tunneling. We find that while Q10 strongly modulates the donor-acceptor distance, it does not exchange energy with Q1. However, excitation in Q29 or Q1 does lead to rapid energy exchange between these modes, which modifies the tunneling rate at early times.

Multidimensional H-atom tunneling in the catecholate monoanion.

We present the catecholate monoanion as a new model system for the study of multidimensional tunneling. It has a symmetrical O-H double-well structure, and the H atom motion between the two wells is coupled to both low and high frequency modes with different strengths. With a view to studying mode-specific tunneling in the catecholate monoanion, we have developed a full (33) dimensional potential energy surface in transition state (TS) normal modes using a Distributed Gaussian Empirical Valence Bond (DGEVB) based approach. We have computed eigenstates in different subspaces using both unrelaxed and relaxed potentials based on the DGEVB model. With unrelaxed potentials, we present results up to 7D subspaces that include the imaginary frequency mode and six modes coupled to it. With relaxed potentials, we focus on the two most important coupling modes. The structures of the ground and vibrationally excited eigenstates are discussed for both approaches and mode-specific tunneling splitting and their trends are presented.

Effect of silver on the phase transition and wettability of titanium oxide films.

The effect of silver on the phase transition and microstructure of titanium oxide films grown by pulsed cathodic arc had been investigated by XRD, SEM and Raman spectroscopy. Following successive thermal annealing up to 1000 °C, microstructural analysis of annealed Ag-TiO2 films reveals that the incorporation of Ag nanoparticles strongly affects the transition temperature from the initial metastable amorphous phase to anatase and stable rutile phase. An increase of silver content into TiO2 matrix inhibits the amorphous to anatase phase transition, raising its temperature boundary and, simultaneously reduces the transition temperature to promote rutile structure at lower value of 600 °C. The results are interpreted in terms of the steric effects produced by agglomeration of Ag atoms into larger clusters following annealing which hinders diffusion of Ti and O ions for anatase formation and constrains the volume available for the anatase lattice, thus disrupting its structure to form rutile phase. The effect of silver on the optical and wetting properties of TiO2 was evaluated to demonstrate its improved photocatalytic performance.