Binding energies of benzene on coinage metal surfaces: Equal stability on different metals

Maaß, Friedrich; Jiang, Yingda; Liu, Wei; Tkatchenko, Alexandre; Tegeder, Petra

doi:10.1063/1.5030094

Cited by 24 publications

(29 citation statements)

References 58 publications

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“…Interestingly, very similar adsorption energies were also reported for structurally simpler aromatic molecules such as benzene on Ag(111) and Au(111). 8,151,152 There, it was argued that the sensitivity of many-body contributions to the planar atomic density of face-centered cubic metals combined with the balance between Pauli repulsion and van der Waals forces between molecules and surface atoms can lead to very similar adsorption energies. 8 Concerning the ILs studied here, we again note that on Au(111), the desorption of the IL WL from Au(111) goes along with a certain degree of decomposition (see above), which could also have an influence on the desorption behavior.…”

Section: Resultsmentioning

confidence: 99%

Stability and Exchange Processes in Ionic Liquid/Porphyrin Composite Films on Metal Surfaces

et al. 2019

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In light of increasing interest in the development of organic–organic multicomponent heterostructures on metals, this molecular-scale study investigates prototypical composite systems of ultrathin porphyrin and ionic liquid (IL) films on metallic supports under well-defined ultrahigh vacuum conditions. By means of angle-resolved X-ray photoelectron spectroscopy, we investigated the adsorption, stability, and thermal exchange of the resulting films after sequential physical vapor deposition of the free-base porphyrin 5,10,15,20-tetraphenylporphyrin, 2H-TPP, and the IL 1-methyl-3-octylimidazolium hexafluorophosphate, [C8C1Im][PF6], on Ag(111) and Au(111). 2H-TPP shows two-dimensional growth of up to two closed molecular layers on Ag(111) and Au(111) and three-dimensional island growth for thicker films. IL films on top of a monolayer of 2H-TPP exhibit Stranski–Krastanov-like growth and are stable up to 385 K. The 2H-TPP layer leads to destabilization of the IL films, compared to the IL in direct contact with the bare metals, by inhibiting the specific adsorption of the ions on the metal surfaces. When the porphyrin is deposited on top of [C8C1Im][PF6] at low temperature, the 2H-TPP molecules adsorb on top of the IL film at first but replace the IL at the IL/metal interfaces upon heating above 240 K. This exchange process is most likely driven by the higher adsorption energy of 2H-TPP on Ag(111) and Au(111) surfaces, as compared to the IL. The behavior observed on Ag(111) and Au(111) is identical. The results are highly relevant for the stability of porphyrin/IL-based thin film catalyst systems and molecular devices, and more generally, stacked organic multilayer architectures.

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Section: Resultsmentioning

confidence: 99%

Stability and Exchange Processes in Ionic Liquid/Porphyrin Composite Films on Metal Surfaces

et al. 2019

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“…These experiments revealed very similar binding energies on Cu, Ag and Au of 15.7, 14.5, and 16.4 kcal/mol, respectively, with error bars of about 1 kcal/mol (based on the back-corrected binding energies of 0.63-0.71 eV). 98 We model the adsorption using a 5×5×3 metal slab with one benzene molecule (low coverage limit) with at least 10Å of vacuum between the metal layers in the 3-D periodic calculations (VASP, see below). Since calculations for these large metallic systems are tedious with a atom-centered basis sets, we conduct the structural optimizations here and in all further examples with the related SCAN-rVV10 functional implemented in VASP with a high plane-wave cutoff of 700 eV and a 3 × 3 × 1 k-point grid.…”

Section: G Adsorption On Polar and Non-polar Surfacesmentioning

confidence: 99%

r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

Hansen¹,

Ehlert²,

Mewes³

2020

Preprint

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The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r2SCAN} is used to construct an efficient composite electronic-structure method termed r2SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r2SCAN functional is combined with a tailor-made triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r2SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r2SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000). In relation to other "3c'' methods, r2SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r2SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.

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“…Depicted at the bottom is the phenol dimer on the left and the ammonia-water dimer on the right. Top right: the benzene molecule adsorption energy to Cu, Ag, and Au surfaces has been shown to be the same, despite the differences in the materials 3,4 . Top left: two evidently distinct buckyball-in-a-ring systems have been shown to have the same stability by Hermann et al 5 …”

Section: Introductionmentioning

confidence: 96%

“…An example of unprecedented complexity is exhibited by benzene adsorption on coinage metals. It was shown using temperature programmed desorption experiments 6–9 that the interaction energy of benzene on gold, copper, and silver is very similar—despite the considerable differences in the surface properties 3,4,10,11 …”

Section: Introductionmentioning

confidence: 99%

Understanding non-covalent interactions in larger molecular complexes from first principles

Al-Hamdani

Tkatchenko

2019

The Journal of Chemical Physics

Self Cite

138

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Non-covalent interactions pervade all matter and play a fundamental role in layered materials, biological systems, and large molecular complexes. Despite this, our accumulated understanding of non-covalent interactions to date has been mainly developed in the tens-of-atoms molecular regime. This falls considerably short of the scales at which we would like to understand energy trends, structural properties, and temperature dependencies in materials where non-covalent interactions have an appreciable role. However, as more reference information is obtained beyond moderately sized molecular systems, our understanding is improving and we stand to gain pertinent insights by tackling more complex systems, such as supramolecular complexes, molecular crystals, and other soft materials. In addition, accurate reference information is needed to provide the drive for extending the predictive power of more efficient workhorse methods, such as density functional approximations that also approximate van der Waals dispersion interactions. In this perspective, we discuss the first-principles approaches that have been used to obtain reference interaction energies for beyond modestly sized molecular complexes. The methods include quantum Monte Carlo, symmetry-adapted perturbation theory, non-canonical coupled cluster theory, and approaches based on the random-phase approximation. By considering the approximations that underpin each method, the most accurate theoretical references for supramolecular complexes and molecular crystals to date are ascertained. With these, we also assess a handful of widely used exchange-correlation functionals in density functional theory. The discussion culminates in a framework for putting into perspective the accuracy of high-level wavefunction-based methods and identifying future challenges.

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Binding energies of benzene on coinage metal surfaces: Equal stability on different metals

Cited by 24 publications

References 58 publications

Stability and Exchange Processes in Ionic Liquid/Porphyrin Composite Films on Metal Surfaces

Stability and Exchange Processes in Ionic Liquid/Porphyrin Composite Films on Metal Surfaces

r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

Understanding non-covalent interactions in larger molecular complexes from first principles

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