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Title: Transition state redox during dynamical processes in semiconductors and insulators

Journal Article · · NPG Asia Materials
 [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States)
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Activation barriers associated with ion diffusion and chemical reactions are vital to understand and predict a wide range of phenomena, such as material growth, ion transport, and catalysis. In the calculation of activation barriers for non-redox processes in semiconductors and insulators, it has been widely assumed that the charge state remains fixed to that of the initial electronic ground state throughout a dynamical process. In this work, we demonstrate that this assumption is generally inaccurate and that a rate-limiting transition state can have a different charge state from the initial ground state. This phenomenon can significantly lower the activation barrier of a dynamical process that depends strongly on charge state, such as carbon vacancy diffusion in 4H-SiC. With inclusion of such transition state redox, the activation barrier varies continuously with Fermi level, in contrast to the step-line feature predicted by the traditional fixed-charge assumption. In this study, a straightforward approach to include the transition state redox effect is provided, the typical situations where the effect plays a significant role are identified, and the relevant electron dynamics are discussed.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543740
Journal Information:
NPG Asia Materials, Journal Name: NPG Asia Materials Journal Issue: 4 Vol. 10; ISSN 1884-4049
Publisher:
Nature Publishing Group AsiaCopyright Statement
Country of Publication:
United States
Language:
English

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