Physisorption controls the conformation and density of states of an adsorbed porphyrin
Conformational changes caused by adsorption can dramatically affect a molecule’s properties. Despite extensive study, however, the exact mechanisms underpinning conformational switching are often unclear. Here we show that the conformation of a prototypical flexible molecule, the freebase tetra(4-br...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Published: |
American Chemical Society
2015
|
| Online Access: | https://eprints.nottingham.ac.uk/31717/ |
| _version_ | 1848794259903217664 |
|---|---|
| author | Jarvis, Samuel Paul Taylor, S. Baran, J.D. Thompson, D. Saywell, Alexander Mangham, Barry Champness, Neil R. Larsson, J.A. Moriarty, Philip |
| author_facet | Jarvis, Samuel Paul Taylor, S. Baran, J.D. Thompson, D. Saywell, Alexander Mangham, Barry Champness, Neil R. Larsson, J.A. Moriarty, Philip |
| author_sort | Jarvis, Samuel Paul |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | Conformational changes caused by adsorption can dramatically affect a molecule’s properties. Despite extensive study, however, the exact mechanisms underpinning conformational switching are often unclear. Here we show that the conformation of a prototypical flexible molecule, the freebase tetra(4-bromophenyl) porphyrin, adsorbed on Cu(111), depends critically on its precise adsorption site and that, remarkably, large conformational changes are dominated by van der Waals interactions between the molecule and the substrate surface. A combination of scanning probe microscopy, single-molecule manipulation, DFT with dispersion density functional theory, and molecular dynamics simulations show that van der Waals forces drive significant distortions of the molecular architecture so that the porphyrin can adopt one of two low-energy conformations. We find that adsorption driven by van der Waals forces alone is capable of causing large shifts in the molecular density of states, despite the apparent absence of chemical interactions. These findings highlight the essential role that van der Waals forces play in determining key molecular properties. |
| first_indexed | 2025-11-14T19:13:21Z |
| format | Article |
| id | nottingham-31717 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:13:21Z |
| publishDate | 2015 |
| publisher | American Chemical Society |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-317172020-05-04T17:22:21Z https://eprints.nottingham.ac.uk/31717/ Physisorption controls the conformation and density of states of an adsorbed porphyrin Jarvis, Samuel Paul Taylor, S. Baran, J.D. Thompson, D. Saywell, Alexander Mangham, Barry Champness, Neil R. Larsson, J.A. Moriarty, Philip Conformational changes caused by adsorption can dramatically affect a molecule’s properties. Despite extensive study, however, the exact mechanisms underpinning conformational switching are often unclear. Here we show that the conformation of a prototypical flexible molecule, the freebase tetra(4-bromophenyl) porphyrin, adsorbed on Cu(111), depends critically on its precise adsorption site and that, remarkably, large conformational changes are dominated by van der Waals interactions between the molecule and the substrate surface. A combination of scanning probe microscopy, single-molecule manipulation, DFT with dispersion density functional theory, and molecular dynamics simulations show that van der Waals forces drive significant distortions of the molecular architecture so that the porphyrin can adopt one of two low-energy conformations. We find that adsorption driven by van der Waals forces alone is capable of causing large shifts in the molecular density of states, despite the apparent absence of chemical interactions. These findings highlight the essential role that van der Waals forces play in determining key molecular properties. American Chemical Society 2015-11-19 Article PeerReviewed Jarvis, Samuel Paul, Taylor, S., Baran, J.D., Thompson, D., Saywell, Alexander, Mangham, Barry, Champness, Neil R., Larsson, J.A. and Moriarty, Philip (2015) Physisorption controls the conformation and density of states of an adsorbed porphyrin. Journal of Physical Chemistry C, 119 (50). pp. 27982-27994. ISSN 1932-7455 http://pubs.acs.org/doi/10.1021/acs.jpcc.5b08350 doi:10.1021/acs.jpcc.5b08350 doi:10.1021/acs.jpcc.5b08350 |
| spellingShingle | Jarvis, Samuel Paul Taylor, S. Baran, J.D. Thompson, D. Saywell, Alexander Mangham, Barry Champness, Neil R. Larsson, J.A. Moriarty, Philip Physisorption controls the conformation and density of states of an adsorbed porphyrin |
| title | Physisorption controls the conformation and density of states of an adsorbed porphyrin |
| title_full | Physisorption controls the conformation and density of states of an adsorbed porphyrin |
| title_fullStr | Physisorption controls the conformation and density of states of an adsorbed porphyrin |
| title_full_unstemmed | Physisorption controls the conformation and density of states of an adsorbed porphyrin |
| title_short | Physisorption controls the conformation and density of states of an adsorbed porphyrin |
| title_sort | physisorption controls the conformation and density of states of an adsorbed porphyrin |
| url | https://eprints.nottingham.ac.uk/31717/ https://eprints.nottingham.ac.uk/31717/ https://eprints.nottingham.ac.uk/31717/ |