Molecular molds for regularizing Kondo states at atom/metal interfaces

Li, Xiangyang; Liang, Zhiting; Li, Bin; Li, Jingcheng; Gao, Pengfei; Yang, Longqing; Zhao, Aidi; Luo, Yi; Hou, J. G.; Zheng, Xiao; Wang, Bing; Yang, Jinlong

doi:10.1038/s41467-020-16402-6

Cited by 32 publications

(30 citation statements)

References 57 publications

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“…71,72 The HEOM approach has been widely used to study a variety of static and dynamic properties of strongly correlated quantum impurity systems in and out of equilibrium. 62,63,[73][74][75][76][77][78][79] In the framework of the HEOM, the influence of the noninteracting leads on the impurity is fully captured by the hybridization functions, Γ α (ω) ≡ π k |t αk | 2 δ(ω − ǫ αk ). For numerical convenience, a Lorentzian form of Γ α (ω) = ∆αW 2 α (ω−Ωα) 2 +W 2 α is adopted, where ∆ α is the effec-tive coupling strength between the impurity and the αth lead, and Ω α and W α are the band center and width of the αth lead, respectively.…”

Section: Introductionmentioning

confidence: 99%

Effect of quantum resonances on local temperature in nonequilibrium open systems

Zeng

Zhang

et al. 2021

Phys. Rev. B

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Measuring local temperatures of open systems out of equilibrium is emerging as a novel approach to study the local thermodynamic properties of nanosystems. An operational protocol has been proposed to determine the local temperature by coupling a probe to the system and then minimizing the perturbation to a certain local observable of the probed system. In this paper, we first show that such a local temperature is unique for a single quantum impurity and the given local observable. We then extend this protocol to open systems consisting of multiple quantum impurities by proposing a local minimal perturbation condition (LMPC). The influence of quantum resonances on the local temperature is elucidated by both analytic and numerical results. In particular, we demonstrate that quantum resonances may give rise to strong oscillations of the local temperature along a multiimpurity chain under a thermal bias.

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Section: Introductionmentioning

confidence: 99%

Effect of quantum resonances on local temperature in nonequilibrium open systems

Zeng

Zhang

et al. 2021

Phys. Rev. B

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“…The rich functionalities of porphyrin complexes orginate from the center macrocycle, which can stablize a variety of elements inside and thus gives rise to distinct structural, electronic, magnetic, optoelectronic, and transport properties [4][5][6][7][8][9][10][11][12][13] . Magnetic metalloporphyrins have been extensively studied by various techniques, exhiting kondo and spin excitation effects, Yu-Shiba bound states, and spin-state switching [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] . Recently, hybridized graphene and metalloporphyrin nanostructures have been achieved, hosting combined intriguing electronic and magnetic properties [28][29][30][31][32][33] .…”

Section: Introductionmentioning

confidence: 99%

Precise Control of π-Electron Magnetism in Metal-Free Porphyrins

Zhao

Jiang

et al. 2020

J. Am. Chem. Soc.

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The porphyrin marcocycle can stabilize a set of magnetic metal ions, thus introducing localized net spins near the center. However, it remains illusive but most desirable to introduce delocalized spins in porphyrins with wide implications, for example, for building correlated quantum spins. Here, we demonstrate that metal-free porphyrins host delocalized -electron magnetism as revealed by scanning probe microscopy and different level of theory calculations. Our results demonstrate that engineering of -electron topologies introduces spin polarized singlet state and delocalized net spins in metal-free porphyrins. In addition, the -electron magnetism can be switched on/off via STM manipulation by tunning the interfacial charge transfer. Our results provide an effective way to precisely control the -electron magnetism in metal-free porphyrins, which can be further extended to design new magnetic functionalities of porphyrin-based architectures.

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“…34 Recently, we have successfully used cobalt phthalocyanine (CoPc) molecules as molds to regularize the local spin states of Co atoms dispersed on an Au(111) surface. 22 It was found that a Co atom captured by a CoPc molecular mold locates either above or beneath an isoindole unit of the Pc ring. In the former case, the Co atom is exposed to the open air, and may thus act as an SAC for CO oxidation.…”

Section: Resultsmentioning

confidence: 99%

“…The DFT+HEOM approach has been successfully applied to describe the Kondo spin-screening effect in magnetic atom adsorbed on the metal support. 22,42,43 Density functional theory calculation. The Perdew-Burke-Ernzerholf (PBE) generalized gradient approximation implemented in the Vienna ab initio simulation package 44 is employed, with the DFT-D3 method of Grimme 45 used to improve the description of van der Waals interactions.…”

Section: Methodsmentioning

confidence: 99%

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Reaction on a Rink: Kondo-Enhanced Heterogeneous Single-Atom Catalysis

Li¹,

Gong²,

Zhuang³

et al. 2021

Preprint

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Boosting the efficiency of heterogeneous single-atom catalysts (SACs) by adjusting the microenvironment of the active atom has recently attracted enormous attention. However, attempts to tune the spin-spin interaction between the SAC and its microenvironment have remained rather scarce. Some interesting questions can be raised, among which a fundamental one is: can the surrounding environment influence the local spin state of an SAC, and if so, can such influence be utilized to enhance the catalytic activity? In this work, we explore such a possibility by investigating the thermochemical effect of Kondo screening of a local atomic spin by free electrons in the metal support. Inspired by the exothermicity of the spin-screening interaction, a novel approach to heterogeneous catalysis -- reaction on a rink (ROAR) -- is proposed. In contrast to the conventional notion of thermal catalytic reaction, lowering the temperature of metal support is predicted to result in a reduced reaction barrier. As a proof of concept, CO oxidation catalyzed by the Co@CoPc/Au(111) composite is scrutinized. By combining the density functional theory and a hierarchical equations of motion approach, it predicts that the existing s-d hybridization between the magnetic d orbital of Co adatom and the substrate metallic states in the transition state will lower the free energy barrier and accelerate the reaction rate. Furthermore, if the strength of s-d hybridization is enlarged, a more appreciable speedup will be achieved. This work highlights the potential usefulness of the spin degrees of freedom to heterogeneous single-atom catalysis, and our proposed ROAR approach could open up a new horizon for exploiting the role of atomic spin in chemical reactions.

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Molecular molds for regularizing Kondo states at atom/metal interfaces

Cited by 32 publications

References 57 publications

Effect of quantum resonances on local temperature in nonequilibrium open systems

Effect of quantum resonances on local temperature in nonequilibrium open systems

Precise Control of π-Electron Magnetism in Metal-Free Porphyrins

Reaction on a Rink: Kondo-Enhanced Heterogeneous Single-Atom Catalysis

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