Real-Time Electron Dynamics Study of Plasmon-Mediated Photocatalysis on an Icosahedral Al13-1 Nanocluster.

Abstract

Nitrogen bond dissociation is one of the important steps in the Haber-Bosch process, where N2 is catalytically converted to NH3; however, the dissociation of the nitrogen triple bond is difficult to achieve. In this study, we investigate the possibility of nitrogen activation using plasmonic excitation of an icosahedral aluminum nanocluster. Real-time time-dependent density functional theory is employed to study the electron dynamics of the Al13-1 and [Al13N2]-1 systems. Step and trapezoidal electric fields with field strengths of 0.001 and 0.01 au and different polarization directions are applied to the systems, and the electron dynamics are analyzed. Because the occupation of nitrogen antibonding orbitals could potentially activate the N-N bond, we investigated the single-particle electronic transitions corresponding to an excitation from an occupied (O) to virtual (V) molecular orbitals (POV) of [Al13N2]-1. We found that N2 antibonding orbitals are more likely to become populated with stronger fields and also by using off-resonance fields.