Ab Initio Analysis of Auger-Assisted Electron Transfer

作者：Hyeon Deuk Kim^*; Kim Joonghan; Prezhdo Oleg V

来源：Journal of Physical Chemistry Letters, 2015, 6(2): 244-249.

DOI：10.1021/jz502505m

Quantum confinement in nanoscale materials allows Auger-type electronhole 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 electronhole and chargephonon 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 donoracceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.

• 出版日期2015-1-15