A multistate Landau–Zener surface hopping model for nonadiabatic dynamics of molecular scattering from metal surfaces

Abstract

Accurate and efficient simulations of nonadiabatic dynamics of molecules scattered from metal surfaces remain a major challenge in theoretical chemistry due to intricate couplings between molecular degrees of freedom and the electronic continuum of metals. In this work, we introduce a multistate Landau–Zener model-based surface hopping (MLZSH) algorithm within the Newns–Anderson Hamiltonian. By treating each crossing independently, the MLZSH approach avoids the expensive calculations of nonadiabatic coupling vectors and the explicit propagation of the electronic wavefunction, compared with the widely used independent electron surface hopping (IESH) method. We benchmark the MLZSH method in two-dimensional and full-dimensional models regarding NO and CO scattering from metal surfaces. MLZSH agrees reasonably well with IESH in most cases and greatly lowers the scaling of the cost with respect to the number of metal orbitals, although it underestimates the nonadiabatic vibrational energy loss when diabatic state crossings are hardly accessed. In addition, MLZSH requires no decoherence corrections. MLZSH is expected to be an efficient tool for simulating many-electron nonadiabatic dynamics at metal surfaces.