Ab-initio molecular dynamic simulation studies: 1. Temperature induced carbon-halogen dissociated reaction and Cα-Cα self-coupling reactions 2. STM-tip induced CO(ads) desorption reaction and their inelastic electron tunneling spectroscopy

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Density functional theory (DFT)-based molecular dynamic simulation in combination with time-resolved simulated reflected infrared adsorption spectroscopy is performed to study 1) the dynamic behavior of catalytic reaction for carbon-halogen dissociation and carbon-carbon self-coupling reaction on metal surface. 2) In addition, we performed our new methodology to generate the inelastic electron tunneling spectroscopy by collecting the dynamic trajectories of local density of state (LDOS) to investigate the STM-tip induced CO desorption reaction. In the part I of my thesis, firstly, we successfully investigate the adsorption behaviours of carbon-halogen rupture reaction for propargyl bromide (HC≡C(β)-C(α)H2Br(ads)) and propynyl iodide (CH3-C(β)≡C(α)-I(ads)) on Ag(111) surface by using DFT-based MD simulation. We found that the carbon-Ag interaction can induce the weakening of carbon-halogen bond due to the delocalization effect between the adsorbed molecule and Ag surface at transition state. In addition, the time-resolved spectra constructed by short-time Fourier transform (STFT) illustrate that the evolution of all the vibrational modes along the carbon-halogen dissociation reaction and have a good agreement with experimental RAIRS results. Secondly, we investigated the thermally induced diffusion processes of different hybridization state of Cα that is, methyl acetylide (CH3-C(β)≡C(α)(ads) : sp hybridization of Cα atom) and ethyl (H3C(β)-C(α)H2(ads) : sp3 hybridization of Cα atom), respectively. Our results indicate that the CH3-C(β)≡C(α)(ads) is very stable due to the strong π-back donation effect as methyl acetylide adsorbed on Ag(111) surface. Therefore the methyl acetylide will have higher diffusion temperature than that of ethyl on the same surface leading to the higher reaction temperature for the Cα-Cα self-coupling reaction. In the part II of my thesis, the DFT-based MD simulation with a Fourier transform of the derivative of local density of states autocorrelation function is introduced to generate the inelastic electron tunnelling spectra for evaluating he effect of STM-tip on adsorption dynamics for CO(ads) on the Ag(110) surface. Based on dynamic results, the STM-tip can induce the desorption process of CO on Ag(110) to produce a functionalized STM-tip (CO-terminated Ag5 cluster tip). By using the STFT, the anharmonic coupling between the frustrated rotation and CO stretching mode can be investigated. Finally, the CO-terminated Ag5 cluster tip can be further used to scan the CoPz (Cobalt porphyrazin) on Ag(110) to generate the local IETS spectrum. Our new methodology successfully observe the frustrated translation of CO vibration senses the spatially varying potential energy landscape of the molecule and its surroundings and have a good agreement with experimental IETS results.