Ab Initio Analysis of Auger-Assisted Electron Transfer.
Quantum confinement in nanoscale materials allows Auger-type electron-hole energy exchange. We show by direct time-domain atomistic simulation and analytic theory that Auger processes give rise to a new mechanism of charge transfer (CT) on the nanoscale. Auger-assisted CT eliminates the renown Marcus inverted regime, rationalizing recent experiments on CT from quantum dots to molecular adsorbates. The ab initio simulation reveals a complex interplay of the electron-hole and charge-phonon channels of energy exchange, demonstrating a variety of CT scenarios. The developed Marcus rate theory for Auger-assisted CT describes, without adjustable parameters, the experimental plateau of the CT rate in the region of large donor-acceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.
†Department of Chemistry, Kyoto University, Kyoto 606-8502, Japan.|‡Japan Science and Technology Agency, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan.
Kim
K
Hyeon-Deuk
§Department of Chemistry, The Catholic University of Korea, Bucheon, Gyunggi-do 420-743, Korea.
Joonghan
J
Kim
∥Department of Chemistry, University of Southern California, 920 Bloom Walk, Los Angeles, California 90089, United States.
Oleg V
OV
Prezhdo
Auger-assisted electron transfer; Fermi’s golden rule; carrier separation; electron−phonon couplings; quantum dots