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Title: Fermi–Löwdin orbital self-interaction correction of adsorption energies on transition metal ions

Journal Article · · Journal of Chemical Physics
DOI: https://doi.org/10.1063/5.0078970 · OSTI ID:1860637
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [2]
  1. Central Michigan Univ., Mount Pleasant, MI (United States); Univ. of Texas at El Paso, TX (United States)
  2. Central Michigan Univ., Mount Pleasant, MI (United States)
  3. Univ. of Pittsburgh, PA (United States)
  4. Temple Univ., Philadelphia, PA (United States)
+ Show Author Affiliations

Density functional theory (DFT)-based descriptions of the adsorption of small molecules on transition metal ions are prone to self-interaction errors. Here, we show that such errors lead to a large over-estimation of adsorption energies of small molecules on Cu+, Zn+, Zn2+, and Mn+ in local spin density approximation (LSDA) and Perdew, Burke, Ernzerhof (PBE) generalized gradient approximation calculations compared to reference values computed using the coupled-cluster with single, doubles, and perturbative triple excitations method. These errors are significantly reduced by removing self-interaction using the Perdew–Zunger self-interaction correction (PZ-SIC) in the Fermi–Löwdin Orbital (FLO) SIC framework. In the case of FLO-PBE, typical errors are reduced to less than 0.1 eV. Furthermore, analysis of the results using DFT energies evaluated on self-interaction-corrected densities [DFT(@FLO)] indicates that the density-driven contributions to the FLO-DFT adsorption energy corrections are roughly the same size in DFT = LSDA and PBE, but the total corrections due to removing self-interaction are larger in LSDA.

Research Organization:
Central Michigan Univ., Mount Pleasant, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE
Grant/Contract Number:
SC0018331
OSTI ID:
1860637
Alternate ID(s):
OSTI ID: 1860538
Journal Information:
Journal of Chemical Physics, Vol. 156, Issue 13; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (44)

Application of accelerated long-range corrected exchange functional [LC-DFT(2Gau)] to periodic boundary condition systems: CO adsorption on Cu(111) surface journal March 2020
Elevating density functional theory to chemical accuracy for water simulations through a density-corrected many-body formalism journal November 2021
On the Question of the Total Energy in the Fermi–Löwdin Orbital Self-Interaction Correction Method journal June 2018
Design of a Metal–Organic Framework with Enhanced Back Bonding for Separation of N 2 and CH 4 journal December 2013
The MRCC program system: Accurate quantum chemistry from water to proteins journal February 2020
Full self-consistency in the Fermi-orbital self-interaction correction journal May 2017
The electronic structure effect in heterogeneous catalysis journal April 2005
Effect of the Perdew–Zunger self-interaction correction on the thermochemical performance of approximate density functionals journal January 2004
Towards efficient density functional theory calculations without self-interaction: The Fermi-Löwdin orbital self-interaction correction journal October 2019
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Single-reference coupled cluster theory for multi-reference problems journal November 2017
Understanding and Reducing Errors in Density Functional Calculations journal August 2013
Localized and canonical atomic orbitals in self‐interaction corrected local density functional approximation journal February 1988
Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride Surfaces journal June 2008
What do the Kohn-Sham Orbital Energies Mean? How do Atoms Dissociate? book
Computational screening study towards redox-active metal-organic frameworks journal November 2013
Understanding Trends in CO 2 Adsorption in Metal–Organic Frameworks with Open-Metal Sites journal February 2014
CO adsorption on the Cu(111) surface: A density functional study journal March 2006
CO 2 Adsorption in M-IRMOF-10 (M = Mg, Ca, Fe, Cu, Zn, Ge, Sr, Cd, Sn, Ba) journal June 2016
Self-interaction correction in water–ion clusters journal March 2021
Towards an Exact Treatment of Exchange and Correlation in Materials: Application to the “CO Adsorption Puzzle” and Other Systems journal April 2007
H2/CO2 separations in multicomponent metal-adeninate MOFs with multiple chemically distinct pore environments journal January 2020
Using scaling relations to understand trends in the catalytic activity of transition metals journal January 2008
Density-related properties from self-interaction corrected density functional theory calculations journal January 2021
Tuning Metal–Organic Frameworks with Open-Metal Sites and Its Origin for Enhancing CO 2 Affinity by Metal Substitution journal March 2012
Designing Open Metal Sites in Metal–Organic Frameworks for Paraffin/Olefin Separations journal August 2019
Fundamental Insights into the Reactivity and Utilization of Open Metal Sites in Cu(I)-MFU-4 l journal August 2019
Rethinking CO adsorption on transition-metal surfaces: Effect of density-driven self-interaction errors journal July 2019
A DFT + Umol model study of the self-interaction error in standard density functional calculations of Ni(CO) m (m = 1–4) journal August 2014
NBO 7.0 : New vistas in localized and delocalized chemical bonding theory journal June 2019
Self-interaction correction to density-functional approximations for many-electron systems journal May 1981
Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction journal July 2019
Fermi orbital derivatives in self-interaction corrected density functional theory: Applications to closed shell atoms journal February 2015
Electronic structure of mononuclear Cu-based molecule from density-functional theory with self-interaction correction journal July 2021
Shrinking Self-Interaction Errors with the Fermi–Löwdin Orbital Self-Interaction-Corrected Density Functional Approximation journal November 2018
Stretched or noded orbital densities and self-interaction correction in density functional theory journal May 2019
The effect of self-interaction error on electrostatic dipoles calculated using density functional theory journal November 2019
Study of self-interaction-errors in barrier heights using locally scaled and Perdew–Zunger self-interaction methods journal January 2022
Multireference Character for 3d Transition-Metal-Containing Molecules journal January 2012
The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors journal October 1970
Natural bond orbital analysis of near‐Hartree–Fock water dimer journal March 1983
How well do self-interaction corrections repair the overestimation of static polarizabilities in density functional calculations? journal January 2021
On the Non‐Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals journal March 1950
Communication: Self-interaction correction with unitary invariance in density functional theory journal March 2014

Figures / Tables (6)

Table I(p. 8)table Table I
Table II(p. 9)table Table II
Figure 1(p. 24)figure Figure 1
Figure 2(p. 25)figure Figure 2
Figure 3(p. 26)figure Figure 3
Figure 4(p. 27)figure Figure 4

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