Title: Reaction-Induced Excitations and Their Effect on Surface Chemistry

Journal Article · · ACS Catalysis
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]
  1. Harvard Univ., Cambridge, MA (United States)
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Despite intensive study of reactions on metals, it is unclear whether electronic excitations play an important role. In this study, we show that nonadiabatic effects do indeed play a significant role in N2 and H2 dissociation on Ru nanoparticles. We employ nonadiabatic dynamical calculations based on real-time, time-dependent density functional theory to study energy dissipation during these exothermic reaction steps. We find that dissipation of the excess energy into excitation of electrons exceeds thermal dissipation into phonons. For isolated dissociation events, electronic friction can increase reaction barriers; furthermore, the excitations induced by a dissociation event can affect other reacting molecules. Our studies suggest that, for exothermic reactions, metal catalysts in reaction conditions may be constantly experiencing electronic excitations, and these excitations can significantly affect surface chemistry.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States); 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), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; SC0012573
OSTI ID:
1543708
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 11 Vol. 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemistry
electronic excitations
energy dissipation
nanoparticles
nonadiabatic dynamics
real-time time-dependent density functional theory