Surface single-molecule dynamics controlled by entropy at low temperatures

J. C. Gehrig, M. Penedo, M. Parschau, J. Schwenk, M. A. Marioni, E. W. Hudson, H. J. Hug

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Configuration transitions of individual molecules and atoms on surfaces are traditionally described using an Arrhenius equation with energy barrier and pre-exponential factor (attempt rate) parameters. Characteristic parameters can vary even for identical systems, and pre-exponential factors sometimes differ by orders of magnitude. Using low-temperature scanning tunnelling microscopy (STM) to measure an individual dibutyl sulfide molecule on Au(111), we show that the differences arise when the relative position of tip apex and molecule changes by a fraction of the molecule size. Altering the tip position on that scale modifies the transition's barrier and attempt rate in a highly correlated fashion, which results in a single-molecular enthalpy-entropy compensation. Conversely, appropriately positioning the STM tip allows selecting the operating point on the compensation line and modifying the transition rates. The results highlight the need to consider entropy in transition rates of single molecules, even at low temperatures.

Original languageEnglish (US)
Article number14404
JournalNature communications
Volume8
DOIs
StatePublished - Feb 9 2017

Fingerprint

Scanning Tunnelling Microscopy
Entropy
entropy
Molecules
Temperature
molecules
Scanning tunneling microscopy
scanning tunneling microscopy
Energy barriers
positioning
sulfides
Enthalpy
apexes
enthalpy
Atoms
configurations
atoms

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

Gehrig, J. C., Penedo, M., Parschau, M., Schwenk, J., Marioni, M. A., Hudson, E. W., & Hug, H. J. (2017). Surface single-molecule dynamics controlled by entropy at low temperatures. Nature communications, 8, [14404]. https://doi.org/10.1038/ncomms14404
Gehrig, J. C. ; Penedo, M. ; Parschau, M. ; Schwenk, J. ; Marioni, M. A. ; Hudson, E. W. ; Hug, H. J. / Surface single-molecule dynamics controlled by entropy at low temperatures. In: Nature communications. 2017 ; Vol. 8.
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Gehrig, JC, Penedo, M, Parschau, M, Schwenk, J, Marioni, MA, Hudson, EW & Hug, HJ 2017, 'Surface single-molecule dynamics controlled by entropy at low temperatures', Nature communications, vol. 8, 14404. https://doi.org/10.1038/ncomms14404

Surface single-molecule dynamics controlled by entropy at low temperatures. / Gehrig, J. C.; Penedo, M.; Parschau, M.; Schwenk, J.; Marioni, M. A.; Hudson, E. W.; Hug, H. J.

In: Nature communications, Vol. 8, 14404, 09.02.2017.

Research output: Contribution to journalArticle

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