Plasmonic metal (typically Au, Ag, and Cu) nanoparticles (MNPs) have extremely important applications in many fields due to their characteristic optical properties such as localized surface plasmon resonance (LSPR). When the incident light induces the collective oscillation of metal free electrons, LSPR occurs in those MNPs. However, this coherent electron oscillation can dephase quickly by nonradiative decay, generating electron-hole pairs with higher energy in non-equilibrium state (i.e., hot carriers) at the timescale of 1-100 fs. During dephasing, the collective dipole moment decreases along with the near-field interaction and scattering probabilities, with the incident energy converted into a hot carrier distribution. When molecules are adsorbed on the metal nanostructure surface, the hot electrons can be transferred to the empty states of adsorbates before thermalization and create a transient negative ion (TNI). With the response of molecular geometry, TNI moves on the excited-state potential energy surface, and therefore their reactive capability is mediated. The plasmon-induced photochemical reactions have different properties from thermal activation, and have the potential to efficiently convert solar energy into chemical energy. In general, there exist two pathways for hot electron transfer, the conventional indirect transfer and the recently proposed direct transfer. In indirect electron transfer process, hot electrons are first generated in the plasmonic metal nanoparticle, then inject into the adsorbate. For direct electron transfer, in the presence of empty hybridized orbitals due to the strong metal-adsorbate coupling, chemical interface damping can induce the plasmon dephasing directly and generate nonthermalized electrons in the empty hybridized orbitals. The plasmon-induced hot carrier transfer has been utilized to foster various photochemistry processes, such as the dissociation of H 2 , 24-26 N 2 , 27 and O 2 , 28,29 CO 2 reduction, water splitting and organic transformations. The solar photocatalytic water splitting is a promising method for hydrogen production. This process usually take place in metal-semiconductor heterojunctions where plasmons enhance photoconversion in the semiconductor via three mechanisms, including light trapping, hot electron/hole transfer, and plasmon-induced resonance energy transfer. The solar water splitting in a Schottky-free junction has been recently found by Robatjazi et al., who observed large photocurrents as a result of direct injection of hot electrons from plasmonic Au NP to molecules. Many theoretical works started to explore the mechanism by investigating the effect of laser intensity and frequency on photocatalytic activity. For example, Meng's group 31 simulated the H 2 O splitting dynamics on Au nanosphere using TDDFT/Ehrenfest dynamics scheme and found the strong correlation between laser intensity, hot electron transfer, and reaction rates. Zhang et.al. focused on the H 2 dissociation induced by Au spheres and found that the dissociation rate of H 2 was closely related to the molecular initial positions. In above two works, the Au particles were identified by the Jellium spheres. The Jellium model is the simplest physical model for the valence electrons, it replaces the real geometry of the metal ionic core by a featureless positively charged background in a finite volume and treats only delocalized electrons explicitly in the mean-field approximation, such as the Hartree-Fock or the local density approximations. The jellium model neglects the lattice structures of metal spheres, and hardly describes the interaction between the metal and adsorbates, and the effect of lattice's vibration. Furthermore, the LSPRs of MNPs are largely dependent on the MNP's shapes and sizes. It is essential to involve those effects in describing plasmon-mediated chemical reactions.