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Related Experiment Video

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Visualizing the Conformational Dynamics of Membrane Receptors Using Single-Molecule FRET

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Re-evaluating how charge transfer modifies the conformation of adsorbed molecules.

P J Blowey¹, S Velari, L A Rochford

¹Physics Department, University of Warwick, Coventry CV4 7AL, UK. D.P.Woodruff@warwick.ac.uk.

|July 28, 2018

Summary

The electron acceptor molecule TCNQ does not bend on silver surfaces as previously thought. Including silver adatoms in calculations is crucial for accurately modeling these metal-organic interfaces.

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Area of Science:

Surface science
Computational chemistry
Materials science

Background:

TCNQ adsorption on coinage metals typically results in a bent molecular structure.
This bent structure is believed to be a consequence of electron transfer and surface interactions.

Purpose of the Study:

To investigate the adsorption structure of TCNQ on Ag(111) using quantitative experimental methods.
To reconcile experimental findings with theoretical predictions using DFT calculations.

Main Methods:

Quantitative experimental structural measurements.
Density Functional Theory (DFT) calculations with dispersion force corrections.
Inclusion of silver adatoms in theoretical models.

Main Results:

TCNQ does not adopt a bent, inverted bowl shape on Ag(111).
Dispersion force corrections in DFT reduce molecule-substrate spacing and predicted bonding.
Accurate structural agreement requires incorporating Ag adatoms into the molecular layer, which is energetically favorable.

Conclusions:

The commonly assumed bent TCNQ structure is incorrect for Ag(111).
Accurate modeling of metal-organic interfaces necessitates both experimental and theoretical approaches.
Re-evaluation of similar previously studied systems is recommended.