Study of electron transfer at semiconductor-liquid interfaces addressing the full system electronic structure Original Research Article

We present new models and simulations for electron transfer (ET) at the semiconductor-liquid interface. Apparently for the first time, we present “first principles” molecular dynamics simulations of this interface which address its full electronic structure (a water /InP/Fe(H2O)2+3+6 ET system is primarily addressed). Our formalism is capable of describing in detail the semiconductor/liquid/redox species system and its real world complications. The shortcomings of conventional models are clearly highlighted. We also report a new Anderson Hamiltonian based ET theory (ABETT) model which includes full energy dependence. We relate our ABETT to molecular orbital theory, compare it to simulation results, and reexamine other ABETTs in light of our findings. We view many fundamental physical features of our models as new. Many are entirely unaccounted for in conventional models of the semiconductor-liquid interface. Our results have quite general implications for solid-liquid interface ET.