Shi, Benjamin X;
Zen, Andrea;
Kapil, Venkat;
Nagy, Peter R;
Gruneis, Andreas;
Michaelides, Angelos;
(2023)
Many-Body Methods for Surface Chemistry Come of Age: Achieving Consensus with Experiments.
Journal of the American Chemical Society
, 145
(46)
pp. 25372-25381.
10.1021/jacs.3c09616.
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Abstract
The adsorption energy of a molecule onto the surface of a material underpins a wide array of applications, spanning heterogeneous catalysis, gas storage, and many more. It is the key quantity where experimental measurements and theoretical calculations meet, with agreement being necessary for reliable predictions of chemical reaction rates and mechanisms. The prototypical molecule-surface system is CO adsorbed on MgO, but despite intense scrutiny from theory and experiment, there is still no consensus on its adsorption energy. In particular, the large cost of accurate many-body methods makes reaching converged theoretical estimates difficult, generating a wide range of values. In this work, we address this challenge, leveraging the latest advances in diffusion Monte Carlo (DMC) and coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] to obtain accurate predictions for CO on MgO. These reliable theoretical estimates allow us to evaluate the inconsistencies in published temperature-programed desorption experiments, revealing that they arise from variations in employed pre-exponential factors. Utilizing this insight, we derive new experimental estimates of the (electronic) adsorption energy with a (more) precise pre-exponential factor. As a culmination of all of this effort, we are able to reach a consensus between multiple theoretical calculations and multiple experiments for the first time. In addition, we show that our recently developed cluster-based CCSD(T) approach provides a low-cost route toward achieving accurate adsorption energies. This sets the stage for affordable and reliable theoretical predictions of chemical reactions on surfaces to guide the realization of new catalysts and gas storage materials.
| Type: | Article |
|---|---|
| Title: | Many-Body Methods for Surface Chemistry Come of Age: Achieving Consensus with Experiments |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/jacs.3c09616 |
| Publisher version: | http://dx.doi.org/10.1021/jacs.3c09616 |
| Language: | English |
| Additional information: | Copyright © 2023 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0. You are free to share (copy and redistribute) this article in any medium or format and to adapt (remix, transform, and build upon) the material for any purpose, even commercially within the parameters below: cc licence Creative Commons (CC): This is a Creative Commons license. Any licence Attribution (BY): Credit must be given to the creator. |
| Keywords: | Science & Technology, Physical Sciences, Chemistry, Multidisciplinary, Chemistry, QUANTUM MONTE-CARLO, DENSITY-FUNCTIONAL-THEORY, ACCURATE ADSORPTION ENERGIES, COUPLED-CLUSTER THEORY, OXIDE SURFACES, CO ADSORPTION, SMALL MOLECULES, GROUND-STATE, CARBON-MONOXIDE, IR-SPECTRA |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Earth Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10187209 |
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