Thermodynamic measurements of adsorption of Xe and CO on NaCl(100)

Hardy, James P.; Ewing, George E.; Stables, R.; Simpson, C.J.S.M.

doi:10.1016/0167-2584(85)91251-4

Cited by 3 publications

(3 citation statements)

References 21 publications

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“…CO adsorption on surfaces of salt crystals such as NaCl has provided an ideal proving ground to study vibrational energy flow among weakly interacting molecules with well-defined separation and orientation . The interaction between the CO adsorbate and the ionic surface is dominated by weak electrostatic (ES) and van der Waals (vdW) interactions, as evidenced by a relatively low adsorption energy and a small CO frequency shift. , For CO in its ground vibrational state, the most stable configuration features carbon-down (C-down) adsorption at the Na + site, thanks to the slightly negative charge in carbon. The adsorbate–substrate interaction is augmented by weak but long-range interadsorbate interactions.…”

Section: Introductionmentioning

confidence: 99%

Potential Energy Landscape of CO Adsorbates on NaCl(100) and Implications in Isomerization of Vibrationally Excited CO

et al. 2020

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Several full-dimensional potential energy surfaces (PESs) are reported for vibrating CO adsorbates at two coverages on a rigid NaCl(100) surface based on first-principles calculations. These PESs reveal a rather flat energy landscape for physisorption of vibrationless CO on NaCl(100), evidenced by various C-down adsorption patterns within a small energy range. Agreement with available experimental results is satisfactory, although quantitative differences exist. These PESs are used to explore isomerization pathways between the C-down and higher-energy O-down configurations, which reveal a significant isomerization barrier. As the CO vibration is excited, however, the energy order of the two isomer changes, which helps to explain the experimental observed flipping of vibrationally excited CO adsorbates.

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Section: Introductionmentioning

confidence: 99%

Potential Energy Landscape of CO Adsorbates on NaCl(100) and Implications in Isomerization of Vibrationally Excited CO

et al. 2020

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“…The experimental adsorption energy is about −186.5 meV, in which the ZPE has been corrected. ,, The results in Table show that CIM-MP2 overestimates the adsorption energy by about 80 meV, while CIM-DLPNO-CCSD(T) offers a significant improvement over CIM-MP2, with deviations around 50 meV from the experimental value. The remaining deviation is possibly from the missing of s- and p- diffusion functions, whose inclusion leads to the convergence difficulty of the periodic HF calculation.…”

Section: Resultsmentioning

confidence: 98%

Cluster-in-Molecule Method Combined with the Domain-Based Local Pair Natural Orbital Approach for Electron Correlation Calculations of Periodic Systems

Wang

Neese

et al. 2022

J. Chem. Theory Comput.

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The cluster-in-molecule (CIM) method was extended to systems with periodic boundary conditions (PBCs) in a previous work (PBC-CIM) [J. Chem. Theory Comput.2019, 15, 2933, which is able to compute the electronic structures of periodic systems at second-order Møller−Plesset perturbation theory (MP2) and coupled cluster singles and doubles (CCSD) levels. However, the high computational costs of CCSD with respect to the size of clusters limit the usage of PBC-CIM to crystals with small or medium unit cells. In this work, we further develop the PBC-CIM method by employing the domain-based local pair natural orbital (DLPNO) methods for the electron correlation calculations of clusters to reduce the computational costs. The combined approach allows CCSD with perturbative triples, denoted as CCSD(T), to be computationally available for accurate descriptions of periodic systems. The distant-pair correction is also implemented to improve the accuracy of PBC-CIM. As in the molecular cases, the distant pair correction significantly improves the accuracy of various PBC-CIM methods with few additional costs. The PBC-CIM-DLPNO-CCSD(T) approach has been applied to investigate the optimized lattice parameter of the cubic LiCl crystal and two adsorption problems (CO on the NaCl(100) surface and H 2 O on the h-BN surface). The results show that the CIM-DLPNO-CCSD(T) method offers accurate and efficient descriptions for the studied systems. Another application to the cohesive energy of the acetic acid crystal reveals that large basis sets are necessary for reliable calculations on the cohesive energies of molecular crystals.

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“…1 The interaction between the CO adsorbate and the ionic surface is dominated by weak electrostatic (ES) and van der Waals (vdW) interactions, as evidenced by a relatively low adsorption energy and a small CO frequency shift. 2,3 For CO in its ground vibrational state, the most stable configuration features carbon-down (C-down) adsorption at the Na + site, 4 thanks to the slightly negative charge in carbon. The adsorbate−substrate interaction is augmented by weak but long-range interadsorbate interactions.…”

Section: Introductionmentioning

confidence: 99%

Potential Energy Landscape of CO Adsorbates on NaCl(100) and Implications in Isomerization of Vibrationally Excited CO

Hariharan¹,

Meyer²,

Guo³

2020

Preprint

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Several full-dimensional potential energy surfaces (PESs) are reported for vibrating CO adsorbates at two coverages on a rigid NaCl(100) surface based on first principles calculations. These PESs reveal a rather flat energy landscape for physisorption of vibrationless CO on NaCl(100), evidenced by various C-down adsorption patterns within a small energy range. Agreement with available experimental results is satisfactory, although quantitative differences exist. These PESs are used to explore isomerization pathways between the C-down and higher energy O-down configurations, which reveal a significant isomerization barrier. As CO vibration is excited, however, the energy order of the two isomer changes, which helps to explain the experimental observed flipping of vibrationally excited CO adsorbates.

show abstract

Thermodynamic measurements of adsorption of Xe and CO on NaCl(100)

Cited by 3 publications

References 21 publications

Potential Energy Landscape of CO Adsorbates on NaCl(100) and Implications in Isomerization of Vibrationally Excited CO

Potential Energy Landscape of CO Adsorbates on NaCl(100) and Implications in Isomerization of Vibrationally Excited CO

Cluster-in-Molecule Method Combined with the Domain-Based Local Pair Natural Orbital Approach for Electron Correlation Calculations of Periodic Systems

Potential Energy Landscape of CO Adsorbates on NaCl(100) and Implications in Isomerization of Vibrationally Excited CO

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