Rice–Ramsperger–Kassel–Marcus
Simulation of Hydrogen Dissociation on Cu(111): Addressing Dynamical
Biases, Surface Temperature, and Tunneling
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Abstract
The effects of dynamics, surface
temperature, and tunneling on
the dissociative chemisorption of hydrogen on Cu(111) are explored
using a dynamically biased precursor-mediated microcanonical trapping
(d-PMMT) model. Transition state vibrational frequencies were taken
from recent generalized gradient approximation density functional
theory (GGA-DFT) electronic structure calculations, and the model’s
few remaining parameters were fixed by optimizing simulations to a
limited number of quantum-state-resolved associative desorption experiments.
The d-PMMT model reproduces a diverse variety of dissociative chemisorption
and associative desorption experimental results and, importantly,
largely captures the surface temperature dependence of quantum-state-resolved
dissociative sticking coefficients. Molecular translational energy
parallel to the surface was treated as a spectator degree of freedom.
The efficacy of molecular rotational energy to promote dissociation,
relative to normal translational energy, varied monotonically from
−45%
to 33% as the rotational energy increased. Efficacies for molecular
vibrational energy and surface phonon energy were 60%. The efficacies
did not vary with isotope change from H<sub>2</sub> to D<sub>2</sub>. The thermal dissociative sticking coefficient for H<sub>2</sub>/Cu(111) is predicted to vary as <i>S</i>(<i>T</i>) = <i>S</i><sub>0</sub> exp(−<i>E</i><sub>a</sub>/<i>RT</i>) where <i>S</i><sub>0</sub> = 0.075 and <i>E</i><sub>a</sub> = 49.2 kJ/mol over the
300 K ≤ <i>T</i> ≤ 1000 K temperature range.
Dynamical effects are significant and suppress <i>S</i>(<i>T</i>) by ∼2 orders of magnitude as compared to statistical
expectations. For thermal dissociative chemisorption of H<sub>2</sub>/Cu(111) at 1000 K, a temperature of catalytic interest, normal translational
energy is calculated to provide 57% of the energy necessary to react,
surface phonons 23%, molecular rotation 15%, and vibration 5%. Tunneling
is calculated to account for 13% of <i>S</i>(<i>T</i>) at 1000 K and more than 50% at temperatures below 400 K. These
results demonstrate that many aspects of gas-surface reactivity can
be modeled using microcanonical transition state theory subject to
a few dynamical constraints