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Spin Controlled Surface Chemistry: Alkyl Desorption from Si(100)-2x1 by Nonadiabatic Hydrogen Elimination

preprint
submitted on 22.03.2020 and posted on 23.03.2020 by Andrew Pohlman, Danil Kaliakin, Sergey Varganov, Sean Casey
An understanding of the role that spin states play in semiconductor surface chemical reactions is currently limited. Herein, we provide evidence of a nonadiabatic reaction involving a localized singlet to triplet thermal excitation of the Si(100) surface dimer dangling bond. By comparing the β-hydrogen elimination kinetics of ethyl adsorbates probed by thermal desorption experiments to electronic structure calculation results, we determined that a coverage-dependent change in mechanism occurs. At low coverage, a nonadiabatic, inter-dimer mechanism is dominant, while adiabatic mechanisms become dominant at higher coverage. Computational results indicate that the spin flip is rapid near room temperature and the nonadiabatic path is accelerated by a barrier that is 40 kJ/mol less than the adiabatic path. Simulated thermal desorption reactions using nonadiabatic transition state theory (NA-TST) for the surface dimer electron spin flip are in close agreement with experimental observations.

Funding

NSF CHE-1654547 (to SAV)

History

Email Address of Submitting Author

scasey@unr.edu

Institution

University of Nevada, Reno

Country

USA

ORCID For Submitting Author

0000-0003-3758-4479

Declaration of Conflict of Interest

The authors declare no conflicts of interest.

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