Home > Research > Publications & Outputs > Physisorption controls the conformation and den...

Research

Associated organisational unit

Links

Text available via DOI:

Keywords

View graph of relations

Physisorption controls the conformation and density of states of an adsorbed porphyrin

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Published

Standard

Physisorption controls the conformation and density of states of an adsorbed porphyrin. / Jarvis, S. P.; Taylor, S.; Baran, J. D. et al.
In: The Journal of Physical Chemistry C, Vol. 119, No. 50, 17.12.2015, p. 27982-27994.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Jarvis, SP, Taylor, S, Baran, JD, Thompson, D, Saywell, A, Mangham, B, Champness, NR, Larsson, JA & Moriarty, P 2015, 'Physisorption controls the conformation and density of states of an adsorbed porphyrin', The Journal of Physical Chemistry C, vol. 119, no. 50, pp. 27982-27994. https://doi.org/10.1021/acs.jpcc.5b08350

APA

Jarvis, S. P., Taylor, S., Baran, J. D., Thompson, D., Saywell, A., Mangham, B., Champness, N. R., Larsson, J. A., & Moriarty, P. (2015). Physisorption controls the conformation and density of states of an adsorbed porphyrin. The Journal of Physical Chemistry C, 119(50), 27982-27994. https://doi.org/10.1021/acs.jpcc.5b08350

Vancouver

Jarvis SP, Taylor S, Baran JD, Thompson D, Saywell A, Mangham B et al. Physisorption controls the conformation and density of states of an adsorbed porphyrin. The Journal of Physical Chemistry C. 2015 Dec 17;119(50):27982-27994. Epub 2015 Nov 19. doi: 10.1021/acs.jpcc.5b08350

Author

Jarvis, S. P. ; Taylor, S. ; Baran, J. D. et al. / Physisorption controls the conformation and density of states of an adsorbed porphyrin. In: The Journal of Physical Chemistry C. 2015 ; Vol. 119, No. 50. pp. 27982-27994.

Bibtex

@article{6fcdff4a11024a458872a236074c0987,
title = "Physisorption controls the conformation and density of states of an adsorbed porphyrin",
abstract = "Conformational changes caused by adsorption can dramatically affect a molecules 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 free-base 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.",
keywords = "GENERAL FORCE-FIELD, INITIO MOLECULAR-DYNAMICS, AUGMENTED-WAVE METHOD, SURFACES, INTERFACES, DISPERSION, SUBSTRATE, CU(111), METALS, METALLOPORPHYRIN",
author = "Jarvis, {S. P.} and S. Taylor and Baran, {J. D.} and D. Thompson and A. Saywell and B. Mangham and Champness, {N. R.} and Larsson, {J. A.} and P. Moriarty",
year = "2015",
month = dec,
day = "17",
doi = "10.1021/acs.jpcc.5b08350",
language = "English",
volume = "119",
pages = "27982--27994",
journal = "The Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "50",

}

RIS

TY - JOUR

T1 - Physisorption controls the conformation and density of states of an adsorbed porphyrin

AU - Jarvis, S. P.

AU - Taylor, S.

AU - Baran, J. D.

AU - Thompson, D.

AU - Saywell, A.

AU - Mangham, B.

AU - Champness, N. R.

AU - Larsson, J. A.

AU - Moriarty, P.

PY - 2015/12/17

Y1 - 2015/12/17

N2 - Conformational changes caused by adsorption can dramatically affect a molecules 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 free-base 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.

AB - Conformational changes caused by adsorption can dramatically affect a molecules 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 free-base 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.

KW - GENERAL FORCE-FIELD

KW - INITIO MOLECULAR-DYNAMICS

KW - AUGMENTED-WAVE METHOD

KW - SURFACES

KW - INTERFACES

KW - DISPERSION

KW - SUBSTRATE

KW - CU(111)

KW - METALS

KW - METALLOPORPHYRIN

U2 - 10.1021/acs.jpcc.5b08350

DO - 10.1021/acs.jpcc.5b08350

M3 - Journal article

VL - 119

SP - 27982

EP - 27994

JO - The Journal of Physical Chemistry C

JF - The Journal of Physical Chemistry C

SN - 1932-7447

IS - 50

ER -