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Title: Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality

Authors:
; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1399814
Grant/Contract Number:
DESC0010499; SC0012575
Resource Type:
Journal Article: Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 44; Related Information: CHORUS Timestamp: 2017-11-20 17:12:58; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Patra, Abhirup, Bates, Jefferson E., Sun, Jianwei, and Perdew, John P. Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality. United States: N. p., 2017. Web. doi:10.1073/pnas.1713320114.
Patra, Abhirup, Bates, Jefferson E., Sun, Jianwei, & Perdew, John P. Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality. United States. doi:10.1073/pnas.1713320114.
Patra, Abhirup, Bates, Jefferson E., Sun, Jianwei, and Perdew, John P. 2017. "Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality". United States. doi:10.1073/pnas.1713320114.
@article{osti_1399814,
title = {Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality},
author = {Patra, Abhirup and Bates, Jefferson E. and Sun, Jianwei and Perdew, John P.},
abstractNote = {},
doi = {10.1073/pnas.1713320114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 44,
volume = 114,
place = {United States},
year = 2017,
month =
}

Journal Article:
Free Publicly Available Full Text
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  • The electronic properties and stabilities of SnO and SnO 2 bulk materials and their low-index surfaces are investigated by density functional theory. An empirical method has been adopted in this study to account for the van der Waals interactions among the Sn-O layers in the bulk and low-index surfaces of SnO . Compared with SnO 2, the structural and electronic properties of SnO bulk and its low-index surfaces present some unique features due to the dual valency of Sn. In SnO , the s orbital of Sn has larger contributions than its p and d orbitals in the first valencemore » band (VB) and the p orbital of Sn has a larger contribution than its s and d orbitals in its conduction band (CB). In SnO 2, the p and d orbitals of Sn play an important role to form the upper part of the VB and its s orbital dominates in forming the lower parts of the VB and the CB. In both oxides, the s orbital of O forms the second VB with lower energy and its p orbitals are involved in forming the first VB and the CB. The calculated bulk modulus and cohesive energy agree well with the experimental measurements. By constructing all possible symmetrical low-index surfaces of SnO and the (111) surface of SnO 2, our results reveal that the calculated surface energies of SnO stoichiometric surfaces are lower than that of the corresponding surfaces of SnO 2 due to different bonding between Sn and O in these two oxides. The calculated stabilities of the low-index stoichiometric surfaces of SnO are in the order (001)>(101)/(011)≥(010)/(100)>(110)>(111) while the order in the case of SnO 2 is (110)>(010)/(100)>(101)/(011)>(001)>(111). The calculated relationships between surface free energies [γ(p,T)] and oxygen chemical potentials [μO(p,T)] indicate that the nonstoichiometric O-terminated (110) and (111) surfaces of SnO could be more stable than their corresponding stoichiometric ones when the μO(p,T) reaches its higher O-rich bound, and one Sn-terminated nonstoichiometric (111) surface of SnO 2 could be more stable than its stoichiometric ones when the μO(p,T) falls into its lower O-poor region. During surface formation from the bulk , the stable surface usually has small atom displacements. For both SnO and SnO 2 the atoms on the (111) surface have larger relaxations than on their other low-index surfaces .« less
  • The hydrogenation of furfural to furfuryl alcohol on Pd(111), Cu(111) and Pt(111) is studied with both standard Density Functional Theory (DFT)-GGA functionals and with van der Waals-corrected density functionals. VdWDF functionals, including optPBE, optB88, optB86b, and Grimme's method, are used to optimize the adsorption configurations of furfural, furfuryl alcohol, and related intermediates resulting from hydrogenation of furfural, and the results are compared to corresponding values determined with GGA functionals, including PW91 and PBE. On Pd(111) and Pt(111), the adsorption geometries of the intermediates are not noticeably different between the two classes of functionals, while on Cu(111), modest changes are seenmore » in both the erpendicular distance and the orientation of the aromatic ringwith respect to the planar surface. In general, the binding energies increase substantially in magnitude as a result of van derWaals contributions on all metals. In contrast, however, dispersion effects on the kinetics of hydrogenation are relatively small. It is found that activation barriers are not significantly affected by the inclusion of dispersion effects, and a Brønsted–Evans–Polanyi relationship developed solely fromPW91 calculations on Pd(111) is capable of describing corresponding results on Cu(111) and Pt(111), even when the dispersion effects are included. Finally, the reaction energies and barriers derived from the dispersion-corrected and pure GGA calculations are used to plot simple potential energy profiles for furfural hydrogenation to furfuryl alcohol on the three considered metals, and an approximately constant downshift of the energetics due to the dispersion corrections is observed.« less