| In this dissertation, we investigate in depth by computational and theoretical methods the processes and behavior of submonolayer electrochemical deposition of Br onto single-crystal Ag(100) electrodes. Although this system has little direct industrial application, it provides a test bed for developing theoretical and computational techniques which can be used to study systems of more applied interest. Br electrodeposited onto a Ag(100) substrate at room temperature displays a disordered phase at low electrochemical potentials. At higher electrochemical potentials, the adlayer undergoes a disorder-order phase transition to a c(2 x 2) ordered phase. The phase transition, the equilibrium properties of the adlayer, and the dynamics of the ordering and disordering processes are studied by a variety computational techniques, including static and dynamic lattice-gas models, an off-lattice equilibrium model, and Langevin simulations. Using a two-dimensional lattice-gas approximation for the adlayer, Monte Carlo simulations are used to explore the equilibrium properties of the Br adlayer under different values of the electrochemical potential. The model predicts the existence of low-temperature phases which are not stable at room temperature. The effects of these low-temperature phases on the room-temperature properties of the adlayer are discussed. Starting from the lattice-gas model developed for equilibrium simulations, a dynamic Monte Carlo simulation program is constructed, and the phase-ordering, disordering, and hysteresis behaviors are studied. The phase-ordering process is in the dynamic universality class known as Model A (Lifshitz-Allen-Cahn dynamics), but the disordering behavior is not as easily classified. Dynamic simulations of cyclic-voltammetry experiments show hysteresis due to kinetic limitations associated with the ordering and disordering processes. To further investigate the properties of the adlayer, the lattice-gas approximation was relaxed and replaced by a corrugation-potential approximation. Within this two-dimensional off-lattice model, the equilibrium properties were found to be similar to those of the lattice-gas model. However, the off-lattice model obviously allows calculations of additional quantities, such as the average lateral displacement from the adsorption site. Langevin dynamic simulations of the off-lattice model were also performed to test the validity of the assumptions used in the dynamic Monte Carlo simulations. However, these dynamic simulations were far too computationally intensive to allow off-lattice simulations of the ordering, disordering, and hysteresis behaviors. As a first step towards developing accelerated simulation methods for off-lattice simulations, we construct an advanced dynamic algorithm for continuum spin systems. |
