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Dynamics of quantum tunneling: Effects on the rate and transition path of OH on Cu(110) Erlend R. M. Davidson,1 Ali Alavi,2 and Angelos Michaelides1
 

Summary: Dynamics of quantum tunneling: Effects on the rate and transition path of OH on Cu(110)
Erlend R. M. Davidson,1 Ali Alavi,2 and Angelos Michaelides1
1London Centre for Nanotechnology and Department of Chemistry, University College London, London WC1E 6BT, United Kingdom
2Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom
Received 27 November 2009; revised manuscript received 26 February 2010; published 23 April 2010
Recent low-temperature scanning-tunneling microscopy experiments T. Kumagai et al., Phys. Rev. B 79,
035423 2009 observed the possible quantum tunneling of hydroxyl groups between two equivalent adsorp-
tion configurations on Cu 110 . Here we analyze the quantum nuclear tunneling dynamics of hydroxyl on
Cu 110 using density-functional theory based techniques. We calculate classical, semiclassical, and quantum-
mechanical transition rates for the flipping of OH between two degenerate energy minima. The classical
transition rate is essentially zero at the temperatures used in experiment and the tunneling rate along the
minimum-energy path is also much too low compared to experimental observations. When tunneling is taken
into account along a direct path connecting the initial and final states with only a minimum amount of the
oxygen movement the transition rate obtained is in much better agreement with experiment, suggesting quan-
tum tunneling effects cause a deviation of the reaction coordinate from the classical transition path.
DOI: 10.1103/PhysRevB.81.153410 PACS number s : 82.20.Xr, 68.43.Bc, 68.35.Ja
The quantum tunneling of hydrogen plays a role in a wide
variety of scientific disciplines, such as the functioning of
enzymes in biological processes,1,2 diffusion through
metals,3 and high-pressure ice,4 to name but a few. Through

  

Source: Alavi, Ali - Department of Chemistry, University of Cambridge

 

Collections: Chemistry