Photodissociation of H$_2$ on Ag and Au Nanoparticles: Effect of Size, and Plasmon versus Inter-Band Transitions on Threshold Intensities for Dissociation (2301.00469v1)

Abstract: This paper provides new insights concerning the simulation of plasmon driven chemical reactions using real-time TDDFT based on the tight-binding electronic structure code DFTB+, with applications to the dissociation of H$_2$ on octahedral silver and gold nanoparticles with 19-489 atoms. A new component of these calculations involves sampling a 300 K canonical ensemble to determine the distribution of possible outcomes of the calculations, and with this approach we are able to determine the threshold for dissociation as a function of laser intensity, wavelength, and nanocluster size. We show that the threshold intensity varies as an inverse power of nanocluster size, which makes it possible to extrapolate the results to sizes that are more typical of experimental studies. The intensities obtained from this extrapolation are around a factor of 100 above powers used in the pulsed experiments. This is a closer comparison of theory and experiment than has been obtained in previous real-time simulations, and the remaining discrepancy can be understood in terms of electromagnetic hot spots that are associated with cluster formation. We also compare the influence of plasmon excitation versus inter-band excitation on reaction thresholds, revealing that for silver clusters plasmon excitation leads to lower thresholds, but for gold clusters, inter-band excitation is more effective. Our study also includes an analysis of charge transfer to and from the H$_2$ molecule, and a determination of orbital populations during and after the pulse, showing the correlation between metal excitations and the location of the antibonding level of H$_2$.