Quantum Influences in the Diffusive Motion of Pyrrole on Cu(111)

Lechner, Barbara A. J.; Hedgeland, Holly; Ellis, John; Allison, W.; Sacchi, Marco; Jenkins, Stephen J.; Hinch, B. J.

doi:10.1002/anie.201208868

Cited by 19 publications

(18 citation statements)

References 25 publications

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“…We also note that the small size of the calculated barriers imply that the molecules should diffuse at relatively low temperatures, despite experimental evidence confirming that the molecules are stable at 77 K (refs 26 , 27 ). In addition to the known difficulties 45 46 47 in determining adsorption energies using vdW-DFT methods, this is potentially due to the absence of zero point energy corrections in our calculations, which has been observed to significantly increase the size of calculated diffusion barriers 48 for single pyrrole molecules (a major constituent of Br 4 TPP). Unfortunately, however, due to the large size of the Br 4 TPP molecule, zero point energy calculations are extremely costly and could not be performed.…”

Section: Resultsmentioning

confidence: 99%

Measuring the mechanical properties of molecular conformers

et al. 2015

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Scanning probe-actuated single molecule manipulation has proven to be an exceptionally powerful tool for the systematic atomic-scale interrogation of molecular adsorbates. To date, however, the extent to which molecular conformation affects the force required to push or pull a single molecule has not been explored. Here we probe the mechanochemical response of two tetra(4-bromophenyl)porphyrin conformers using non-contact atomic force microscopy where we find a large difference between the lateral forces required for manipulation. Remarkably, despite sharing very similar adsorption characteristics, variations in the potential energy surface are capable of prohibiting probe-induced positioning of one conformer, while simultaneously permitting manipulation of the alternative conformational form. Our results are interpreted in the context of dispersion-corrected density functional theory calculations which reveal significant differences in the diffusion barriers for each conformer. These results demonstrate that conformational variation significantly modifies the mechanical response of even simple porpyhrins, potentially affecting many other flexible molecules.

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Section: Resultsmentioning

confidence: 99%

Measuring the mechanical properties of molecular conformers

et al. 2015

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“…In our previous work we benchmarked the performance of the original TS scheme, as implemented in CASTEP, on several aromatic systems: pyrrole/Cu(111), 7 thiophene/Cu(111) 6 and benzene/Cu(001). 6 For pyrrole and thiophene the surface translational/rotational barriers are in very good agreement with the experimental results obtained by HeSE spectroscopy.…”

Section: Computational Resultsmentioning

confidence: 99%

“…In previous works we have explored the dynamics of the cyclopentadienyl anion (Cp), pyrrole and thiophene adsorbed on the same Cu(111) surface. 6 – 9 The combination of state of the art helium spin-echo spectroscopy (HeSE) and density functional theory calculations has provided insight into the role of charge transfer and ionic binding in aromatic adsorption, 8 , 9 and the contribution of rotational, 6 vibrational 7 and other external degrees of freedom 10 to molecular transport on surfaces.…”

Section: Introductionmentioning

confidence: 99%

The dynamics of benzene on Cu(111): a combined helium spin echo and dispersion-corrected DFT study into the diffusion of physisorbed aromatics on metal surfaces

Sacchi

Singh²,

Chisnall

et al. 2017

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We use helium spin-echo spectroscopy (HeSE) to investigate the dynamics of the diffusion of benzene adsorbed on Cu(111). The results of these measurements show that benzene moves on the surface through an activated jump-diffusion process between the adsorption sites on a Bravais lattice. Density Functional Theory (DFT) calculations with van der Waals (vdW) corrections help us understand that the molecule diffuses by jumping through non-degenerate hollow sites. The results of the calculations shed light on the nature of the binding interaction between this prototypical aromatic molecule and the metallic surface. The highly accurate HeSE experimental data provide a quantitatively stringent benchmark for the vdW correction schemes applied to the DFT calculations and we compare the performances of several dispersion interaction schemes.

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“…As theorists strive to reach "chemical accuracy" with state-of-the-art calculation methods [1][2][3], it is increasingly important to obtain high-precision experimental results that can be used as definitive benchmark data to evaluate these methods [4][5][6][7]. In many fields of science and technology, the development of ever more accurate ab initio theoretical methods significantly reduces the time required to tailor and characterize new materials.…”

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confidence: 99%

Ultra-high precision determination of site energy differences using a Bayesian method

et al. 2014

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How to cite:Lechner, B. A. J.; Kole, P. R.; Hedgeland, H.; Jardine, A. P.; Allison, W.; Hinch, B. J. and Ellis, J. (2014). Ultra-high precision determination of site energy differences using a Bayesian method. Physical Review B, 89(12) For guidance on citations see FAQs. Accurate experimental data of adsorbate potential energy landscapes are crucial as benchmarks for the evaluation of first-principles calculations. Here, we present a Bayesian method, analyzing the difference in forward and backward hopping rate in helium spin-echo measurements, that allows us to determine the binding-energy difference between two sites with unprecedented accuracy. Demonstrating the power of the method on the model system cyclopentadienyl/Cu(111), we find an energy difference between fcc and hcp hollow sites of (10.6 ± 1.7) meV.

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Quantum Influences in the Diffusive Motion of Pyrrole on Cu(111)

Cited by 19 publications

References 25 publications

Measuring the mechanical properties of molecular conformers

Measuring the mechanical properties of molecular conformers

The dynamics of benzene on Cu(111): a combined helium spin echo and dispersion-corrected DFT study into the diffusion of physisorbed aromatics on metal surfaces

Ultra-high precision determination of site energy differences using a Bayesian method

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