Structure and infrared absorption of the first layer C2H2 on the NaCl(100) single-crystal surface

Cabello-Cartagena, A. G.; Vogt, Jochen; Weiß, Helmut

doi:10.1063/1.3319787

Cited by 12 publications

(14 citation statements)

References 32 publications

(44 reference statements)

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“…Experimental values for the adsorption energy are À5.7 kcal mol À1 and À7.1 kcal mol À1 , [35,37] where the latter value corresponds to an experimental desorption enthalpy at half coverage. To the best of our knowledge, adsorption distances have not been measured experimentally, but previous theoretical investigations predict an equilibrium distance of about 3 .…”

Section: Adsorption Of Acetylene On Sodium Chloridementioning

confidence: 99%

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System‐Dependent Dispersion Coefficients for the DFT‐D3 Treatment of Adsorption Processes on Ionic Surfaces

et al. 2011

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Dispersion-corrected density functional theory calculations (DFT-D3) were performed for the adsorption of CO on MgO and C(2) H(2) on NaCl surfaces. An extension of our non-empirical scheme for the computation of atom-in-molecules dispersion coefficients is proposed. It is based on electrostatically embedded M(4)X(4) (M=Na, Mg) clusters that are used in TDDFT calculations of dynamic dipole polarizabilities. We find that the C(MM)(6) dispersion coefficients for bulk NaCl and MgO are reduced by factors of about 100 and 35 for Na and Mg, respectively, compared to the values of the free atoms. These are used in periodic DFT calculations with the revPBE semi-local density functional. As demonstrated by calculations of adsorption potential energy curves, the new C(6) coefficients lead to much more accurate energies (E(ads)) and molecule-surface distances than with previous DFT-D schemes. For NaCl/C(2) H(2) we obtained at the revPBE-D3(BJ) level a value of E(ads) =-7.4 kcal mol(-1) in good agreement with experimental data (-5.7 to -7.1 kcal mol(-1)). Dispersion-uncorrected DFT yields an unbound surface state. For the MgO/CO system, the computed revPBE-D3(BJ) value of E(ads) =-4.1 kcal mol(-1) is also in reasonable agreement with experimental results (-3.0 kcal mol(-1)) when thermal corrections are taken into account. Our new dispersion correction also improves computed lattice constants of the bulk systems significantly compared to plain DFT or previous DFT-D results. The extended DFT-D3 scheme also provides accurate non-covalent interactions for ionic systems without empirical adjustments and is suggested as a general tool in surface science.

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Section: Adsorption Of Acetylene On Sodium Chloridementioning

confidence: 99%

“…[31,[35][36][37] This system was chosen to test the new dispersion coefficients for ionic materials in a typical application. The unit cell for a full-coverage adsorption is shown in Figure 1.…”

Section: Adsorption Of Acetylene On Sodium Chloridementioning

confidence: 99%

System‐Dependent Dispersion Coefficients for the DFT‐D3 Treatment of Adsorption Processes on Ionic Surfaces

et al. 2011

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“…8,15,16,28,29 Because the dipole moment involved with the ν 3 mode of CO 2 is parallel to its molecular axis, direct structural information is obtained in this way. The A s /A p ratio is plotted in Figure 6 as a function of the tilt angle θ of a dipole moment with respect to the surface plane.…”

Section: ' Introductionmentioning

confidence: 99%

Structure of CO₂ Adsorbed on the KCl(100) Surface

et al. 2011

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The structure and dynamics of the adsorbate CO(2)/KCl(100) from a diluted phase to a saturated monolayer have been investigated with He atom scattering (HAS), low-energy electron diffraction (LEED), and polarization dependent infrared spectroscopy (PIRS). Two adsorbate phases with different CO(2) coverage have been found. The low-coverage phase is disordered at temperatures near 80 K and becomes at least partially ordered at lower temperatures, characterized by a (2√2×√2)R45° diffraction pattern. The saturated 2D phase has a high long-range order and exhibits (6√2×√2)R45° symmetry. Its isosteric heat of adsorption is 26 ± 4 kJ mol(-1). According to PIRS, the molecules are oriented nearly parallel to the surface, the average tilt angle in the saturated monolayer phase is 10° with respect to the surface plane. For both phases, structure models are proposed by means of potential calculations. For the saturated monolayer phase, a striped herringbone structure with 12 inequivalent molecules is deduced. The simulation of infrared spectra based on the proposed structures and the vibrational exciton approach gives reasonable agreement between experimental and simulated infrared spectra.

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“…The adsorption of acetylene on sodium chloride was studied by Dunn and Cabello, who provide adsorption energies of 5.7 kcl/mol and 7.4 kcal/mol for full and half coverage, respectively. 109,110 We employ a model system taken from ref. 111, which corresponds to full coverage with the C 2 H 2 molecules ordered in a T-shaped formation.…”

Section: G Adsorption On Polar and Non-polar Surfacesmentioning

confidence: 99%

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

Grimme¹,

Hansen²,

Ehlert³

et al. 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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Structure and infrared absorption of the first layer C2H2 on the NaCl(100) single-crystal surface

Cited by 12 publications

References 32 publications

System‐Dependent Dispersion Coefficients for the DFT‐D3 Treatment of Adsorption Processes on Ionic Surfaces

System‐Dependent Dispersion Coefficients for the DFT‐D3 Treatment of Adsorption Processes on Ionic Surfaces

Structure of CO₂ Adsorbed on the KCl(100) Surface

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

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Structure and infrared absorption of the first layer C2H2 on the NaCl(100) single-crystal surface

Cited by 12 publications

References 32 publications

System‐Dependent Dispersion Coefficients for the DFT‐D3 Treatment of Adsorption Processes on Ionic Surfaces

System‐Dependent Dispersion Coefficients for the DFT‐D3 Treatment of Adsorption Processes on Ionic Surfaces

Structure of CO2 Adsorbed on the KCl(100) Surface

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

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Structure of CO₂ Adsorbed on the KCl(100) Surface