Fig. 2: Topography of three PESs.
a Comparison of energies along the minimum energy path of NO dissociation on Au(111) on the ground revPBE, PW9135, and previous RST23 PESs. The green arrow indicates the vibrational energy of NO(v = 16) in our simulations. Two-dimensional cuts of the b revPBE, c PW91, and d RST ground state PESs as a function of rNO and ZNO, with two angles (θ and φ, defined in Supplementary Fig. 1) optimized and other coordinates fixed at the dissociation transition state. The energy is given relative to a free NO molecule far from the surface, in units of eV. A representative IESH trajectory, with the black line representing the incoming component and the magenta line representing the outgoing component, is projected onto the corresponding PES. The crossing seam (blue dashed line) between two diabatic states and the transition state (red “T”) are also shown on the PES. Note that this crossing seam is derived from the orientation that facilitates the most efficient electron transfer, where the NO molecule is perpendicularly placed on the hcp site with the N atom pointing to the surface. Source data are provided in a Source data file.
