VO2 is renowned for its electric transition from an insulating monoclinic (M1) phase, characterized by V–V dimerized structures, to a metallic rutile (R) phase above 340 K. This transition is accompanied by a magnetic change: the M1 phase exhibits a non-magnetic spin-singlet state, while the R phase exhibits a state with local magnetic moments. Simultaneous simulation of the structural, electric, and magnetic properties of this compound is of fundamental importance, but the M1 phase alone has posed a significant challenge to the density functional theory (DFT). In this study, we show none of the commonly used DFT functionals, including those combined with on-site Hubbard U to treat 3d electrons better, can accurately predict the V–V dimer length. The spin-restricted method tends to overestimate the strength of the V–V bonds, resulting in a small V–V bond length. Conversely, the spin-symmetry-breaking method exhibits the opposite trends. Each of these two bond-calculation methods underscores one of the two contentious mechanisms, i.e., Peierls lattice distortion or Mott localization due to electron–electron repulsion, involved in the metal–insulator transition in VO2. To elucidate the challenges encountered in DFT, we also employ an effective Hamiltonian that integrates one-dimensional magnetic sites, thereby revealing the inherent difficulties linked with the DFT computations.
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7 April 2024
Research Article|
April 01 2024
Challenges for density functional theory in simulating metal–metal singlet bonding: A case study of dimerized VO2 Available to Purchase
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John Perdew Festschrift
Yubo Zhang
;
Yubo Zhang
a)
(Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Visualization, Writing – original draft, Writing – review & editing)
1
Minjiang Collaborative Center for Theoretical Physics, College of Physics and Electronic Information Engineering, Minjiang University
, Fuzhou, China
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Da Ke;
Da Ke
(Formal analysis)
1
Minjiang Collaborative Center for Theoretical Physics, College of Physics and Electronic Information Engineering, Minjiang University
, Fuzhou, China
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Junxiong Wu
;
Junxiong Wu
(Formal analysis)
1
Minjiang Collaborative Center for Theoretical Physics, College of Physics and Electronic Information Engineering, Minjiang University
, Fuzhou, China
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Chutong Zhang;
Chutong Zhang
(Formal analysis)
1
Minjiang Collaborative Center for Theoretical Physics, College of Physics and Electronic Information Engineering, Minjiang University
, Fuzhou, China
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Lin Hou
;
Lin Hou
(Formal analysis)
2
Department of Physics and Engineering Physics, Tulane University
, New Orleans, Louisiana 70118, USA
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Baichen Lin
;
Baichen Lin
(Formal analysis)
3
School of Materials Science and Engineering, Nanyang Technological University
, Singapore 639798, Republic of Singapore
4
Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR)
, Singapore 138634, Republic of Singapore
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Zuhuang Chen
;
Zuhuang Chen
(Formal analysis)
5
School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen
, Shenzhen 518055, China
6
Flexible Printed Electronics Technology Center, Harbin Institute of Technology, Shenzhen
, Shenzhen 518055, China
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John P. Perdew
;
John P. Perdew
(Formal analysis, Investigation, Supervision, Writing – original draft, Writing – review & editing)
2
Department of Physics and Engineering Physics, Tulane University
, New Orleans, Louisiana 70118, USA
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Jianwei Sun
Jianwei Sun
a)
(Formal analysis, Investigation, Supervision, Writing – original draft, Writing – review & editing)
2
Department of Physics and Engineering Physics, Tulane University
, New Orleans, Louisiana 70118, USA
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Yubo Zhang
1,a)
Da Ke
1
Junxiong Wu
1
Chutong Zhang
1
Lin Hou
2
Baichen Lin
3,4
Zuhuang Chen
5,6
John P. Perdew
2
Jianwei Sun
2,a)
1
Minjiang Collaborative Center for Theoretical Physics, College of Physics and Electronic Information Engineering, Minjiang University
, Fuzhou, China
2
Department of Physics and Engineering Physics, Tulane University
, New Orleans, Louisiana 70118, USA
3
School of Materials Science and Engineering, Nanyang Technological University
, Singapore 639798, Republic of Singapore
4
Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR)
, Singapore 138634, Republic of Singapore
5
School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen
, Shenzhen 518055, China
6
Flexible Printed Electronics Technology Center, Harbin Institute of Technology, Shenzhen
, Shenzhen 518055, China
J. Chem. Phys. 160, 134101 (2024)
Article history
Received:
October 09 2023
Accepted:
March 03 2024
Citation
Yubo Zhang, Da Ke, Junxiong Wu, Chutong Zhang, Lin Hou, Baichen Lin, Zuhuang Chen, John P. Perdew, Jianwei Sun; Challenges for density functional theory in simulating metal–metal singlet bonding: A case study of dimerized VO2. J. Chem. Phys. 7 April 2024; 160 (13): 134101. https://doi.org/10.1063/5.0180315
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