Header

UZH-Logo

Maintenance Infos

Zooming in on the O–O Bond Formation—An Ab Initio Molecular Dynamics Study Applying Enhanced Sampling Techniques


Schilling, Mauro; Cunha, Richard A; Luber, Sandra (2020). Zooming in on the O–O Bond Formation—An Ab Initio Molecular Dynamics Study Applying Enhanced Sampling Techniques. Journal of Chemical Theory and Computation, 16(4):2436-2449.

Abstract

Mastering artificial water oxidation is a key step on moving away from fossil fuels toward a carbon emission-free society. Unfortunately, the crucial chemical transformation of this reaction, the O–O bond formation, is still not well understood, even though there are various known active water oxidation catalysts, such as Ru-based catalysts bearing a Py5 ligand. Those were recently investigated both experimentally and using a static density functional theory (DFT) approach based on geometry optimizations. In this work, we shed light on the O–O formation catalyzed by those Ru-based complexes, utilizing enhanced sampling techniques such as the Bluemoon ensemble and metadynamics together with high-performance DFT-based molecular dynamics simulations. This allowed unprecedented detailed insights into the process of the oxygen–oxygen bond formation and also extended the view on the reaction network and the flexibility of the product state because of the consideration of the dynamics at ambient conditions. Our model system contained both the catalyst and a large number of explicit water molecules which can participate in the reaction and stabilize intermediates. Moreover, it is demonstrated how crucial the choice of the collective variable is in order to capture relevant features of the studied reaction.

Abstract

Mastering artificial water oxidation is a key step on moving away from fossil fuels toward a carbon emission-free society. Unfortunately, the crucial chemical transformation of this reaction, the O–O bond formation, is still not well understood, even though there are various known active water oxidation catalysts, such as Ru-based catalysts bearing a Py5 ligand. Those were recently investigated both experimentally and using a static density functional theory (DFT) approach based on geometry optimizations. In this work, we shed light on the O–O formation catalyzed by those Ru-based complexes, utilizing enhanced sampling techniques such as the Bluemoon ensemble and metadynamics together with high-performance DFT-based molecular dynamics simulations. This allowed unprecedented detailed insights into the process of the oxygen–oxygen bond formation and also extended the view on the reaction network and the flexibility of the product state because of the consideration of the dynamics at ambient conditions. Our model system contained both the catalyst and a large number of explicit water molecules which can participate in the reaction and stabilize intermediates. Moreover, it is demonstrated how crucial the choice of the collective variable is in order to capture relevant features of the studied reaction.

Statistics

Citations

Altmetrics

Downloads

1 download since deposited on 07 Apr 2020
1 download since 12 months
Detailed statistics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Computer Science Applications
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Computer Science Applications
Language:English
Date:14 April 2020
Deposited On:07 Apr 2020 09:04
Last Modified:22 Apr 2020 23:22
Publisher:American Chemical Society (ACS)
ISSN:1549-9618
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.jctc.9b01207
Project Information:
  • : FunderLightChEC
  • : Grant ID
  • : Project Title
  • : FunderSNF
  • : Grant IDPP00P2 170667
  • : Project Title

Download

Closed Access: Download allowed only for UZH members