An ab initio path integral treatment of hydrogenation reactions at metal surfaces
Lead Research Organisation:
University College London
Department Name: London Centre for Nanotechnology
Abstract
The making and breaking of bonds involving hydrogen atoms at metal surfaces is the bread and butter of heterogeneous catalysis. Water formation from its elements, for example, proceeds through the cleavage of the H-H bond in the H2 molecule followed by subsequent hydrogenation reactions of atomic oxygen and hydroxyl to yield water. The role quantum nuclear effects - such as tunnelling and quantum delocalization - play in determining the mechanisms and rates of these processes remains largely unexplored. This is true despite knowledge that the quantum nuclear effects of hydrogen can be significant at room temperature and below and despite the growing economic and environmental needs to better understand and exploit catalysis at increasingly low temperatures. Here we plan to make a start at addressing this situation with state-of-the-art first principles electronic structure approaches. Specifically ab initio path integral techniques will be developed and applied to rigorously explore the role quantum nuclear effects play in elementary diffusion processes and reaction events involving hydrogen at metal surfaces, culminating in the fully quantum ab initio treatment of the water formation reaction on Pt. This is a highly adventurous yet feasible project. The methodological developments proposed here require the involvement of a post-doc, which is requested for the three year lifetime of the project. Likewise this project will rely heavily on the UK's next generation terascale high performance computing facility (HECToR), and, indeed, only now with the imminent installation of HECToR does this highly computationally demanding project become feasible in the UK.
Organisations
Publications
Li X
(2011)
Quantum nature of the hydrogen bond
in Proceedings of the National Academy of Sciences
Li XZ
(2010)
Quantum nature of the proton in water-hydroxyl overlayers on metal surfaces.
in Physical review letters
Ma J
(2009)
The water-benzene interaction: insight from electronic structure theories.
in The Journal of chemical physics
Walker B
(2010)
Direct assessment of quantum nuclear effects on hydrogen bond strength by constrained-centroid ab initio path integral molecular dynamics.
in The Journal of chemical physics
Zhang C
(2011)
Quantum nuclear effects on the location of hydrogen above and below the palladium (100) surface
in Surface Science
Description | New insight into the quantum nature of hydrogen at interfaces. |
Exploitation Route | Application of the techniques developed and approaches employed to other systems |
Sectors | Aerospace Defence and Marine Education Electronics |
URL | http://www.chem.ucl.ac.uk/ice |
Description | ERC Consolidator Grant |
Amount | € 1,000,000 (EUR) |
Organisation | European Research Council (ERC) |
Sector | Public |
Country | Belgium |
Start | 03/2014 |
End | 03/2019 |
Description | Royal Society Wolfs Merit Award |
Amount | £75,000 (GBP) |
Organisation | The Royal Society |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 03/2012 |
End | 03/2017 |