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    Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Park Park Park Park Park Park Park Park

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    Alex-Mihai Ciubara
    1) The document summarizes a study that uses density functional theory to examine how depositing a Mn12 single-molecule magnet monolayer on a gold surface affects its electronic structure and magnetic properties. 2) It finds that the gold surface causes orbital broadening and a transfer of 1.23 electrons from the gold to the manganese atoms. 3) Despite changes in charge and orbital broadening, the magnetic anisotropy barrier of the Mn12 molecule remains almost unchanged after deposition on the gold surface.

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    Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Park Park Park Park Park Park Park Park

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    Alex-Mihai Ciubara
    46 views39 pages
    1) The document summarizes a study that uses density functional theory to examine how depositing a Mn12 single-molecule magnet monolayer on a gold surface affects its electronic structure and magnetic properties. 2) It finds that the gold surface causes orbital broadening and a transfer of 1.23 electrons from the gold to the manganese atoms. 3) Despite changes in charge and orbital broadening, the magnetic anisotropy barrier of the Mn12 molecule remains almost unchanged after deposition on the gold surface.

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    1) The document summarizes a study that uses density functional theory to examine how depositing a Mn12 single-molecule magnet monolayer on a gold surface affects its electronic structure and magnetic properties. 2) It finds that the gold surface causes orbital broadening and a transfer of 1.23 electrons from the gold to the manganese atoms. 3) Despite changes in charge and orbital broadening, the magnetic anisotropy barrier of the Mn12 molecule remains almost unchanged after deposition on the gold surface.

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    46 views39 pages

    Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Kyungwha Park Park Park Park Park Park Park Park

    Uploaded by

    Alex-Mihai Ciubara
    1) The document summarizes a study that uses density functional theory to examine how depositing a Mn12 single-molecule magnet monolayer on a gold surface affects its electronic structure and magnetic properties. 2) It finds that the gold surface causes orbital broadening and a transfer of 1.23 electrons from the gold to the manganese atoms. 3) Despite changes in charge and orbital broadening, the magnetic anisotropy barrier of the Mn12 molecule remains almost unchanged after deposition on the gold surface.

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    of 39

    Interaction between a singlesingle-molecule magnet Mn12 monolayer and a gold surface

    Kyungwha Park
    Department of Physics, Virginia Tech

    Salvador BarrazaBarraza-Lopez (postdoc) Michael C. Avery (undergraduate)

    Supported by Jeffress Memorial Trust Fund NCSA clusters, Virginia Tech System X, VT clusters

    Outline
    What are single-molecule magnets (SMMs)? Motivation Methodology: density-functional theory (DFT) Review of properties of isolated SMM Mn12 SMM Mn12 deposited on a gold surface
    - Method and model - Changes in electronic structure (orbital broadening, charge transfer) - Changes in magnetic properties

    Beyond DFT: effect of Hubbard-like U term

    What are singlesingle-molecule magnets?


    Volume of one molecule: a few nm3 Single molecule: several transition metal ions strongly coupled via ligands Behaves as single-domain magnetic nanoparticle Large spin with large magnetization reorientation barrier Can form single crystals (different molecules are well separated)
    C & E news, Dec 13, 2004 T.Lis Acta Cryst. B36, 2042 (1980)

    Mn12

    1.5nm S=10

    Mn4

    Mn3+ Mn4+ O

    Cl N C

    S=9/2

    Examples: Mn12 , Mn4 , Fe4, Fe8, Co4, Ni4, cyanide-bridged molecules, Mn84 D. Hendrickson J. Am. Chem. Soc. 114, 2455 (1992) torus, etc.

    SingleSingle -molecule magnets


    Fe8 S=10 Mn5N3 S=11 Mn84 torus
    Wieghart et al., Angew. Chem. Int. Ed. Engl. 23, 77 (1984)

    S=6

    Fe2Ni2

    C.-I. Yang et al., J. Am. Chem. Soc. 129, 456 (2007)

    Tasiopoulos et al, Angew. Chem. Int. Ed. 43, 2117 (2004)

    Single-chain magnet Mn-Ni-Mn unit S=3 S=3


    Li et al., Inorg. Chem. 44, 4903 (2005) Coulon et al., PRB 69, 132408 (2004)

    Magnetic Anisotropy Barrier & Easy Axis


    (magnetization reversal barrier) Classical
    Energy
    caused by spin-orbit coupling
    easy axis

    Quantum mechanical
    Energy = Dms2 ; D > 0 for B=0
    Spin projection ms

    Barrier

    Energy

    S=10

    Barrier "down" Easy axis


    e.g. Mn12 : Barrier = 60K

    "up"

    Magnetic hysteresis: essence of quantum tunneling


    On resonance

    Mn12 (S=10) at 1.9K


    0.04T/s
    per data point

    In ground state

    Ms
    down up

    tobs=500 s

    Steps: tunneling on Plateaus: tunneling off Classical ferromagnets at 300 K HL (T) Off resonance down up

    B. Barbara et al., J. Phys. Soc. Jpn. (2000); J. Friedman et al., PRL (1996); L. Thomas et al., Nature (1996)

    Another evidence of quantum tunneling


    Time dependence of magnetization becomes independent of temperature (T) as T 0
    [log(/ 0 )]1

    = 0 exp(U/ kBT),

    C. Paulsen et al., J. Mag. Mag. Mat. (1995) A. Caneschi et al., Nature (1993)

    Motivation: device applications


    Deposition of SMMs on a gold or silicon surface
    Steckel et al., Nano Lett. (2004); Zobbi et al, Chem. Comm. (2005); Fleury et al., Chem. Comm. (2005).

    Magnetic measurement:
    Properties of Mn12 monolayers differ from those of bulk Mn12
    Naitabdi et al., Adv. Mater. 17. 1612 (2005) Salman et al., Nano Lett. (2007)

    Photoemission spectra on Mn12 monolayers: Mn12 d orbitals in valence


    bands are similar to those for bulk Mn12

    STM image

    del Pennino et al., Surf. Sci. (2006); Voss et al., PRB (2007)

    Motivation: device applications


    Electronic transport measurements through SMM Mn12

    - Jo at el. Nano Lett (2006)

    - Henderson et al., J. Appl. Phys. (2007)

    Theories on transport through SMM:


    - G.H. Kim and T.S. Kim, PRL (2004). - Romeike et al. PRLs (2006) - Elste and Timm, PRB (2005), PRBs (2006) - Leuenberger and Mucciolo, PRL 97, 126601 (2006). - Misiorny and Barnas, cond-mat/0706.2315

    No first-principles calculations on SMMs deposited on a surface or bridged between electrodes

    How to solve manymany-body problems quantum mechanically using DensityDensity-Functional Theory(DFT)


    Interacting many-electron problem: H=E where =(x1,y1,z1,...,xN,yN,zN) H = Hkin + Hn-e + He-e Cost: M3N for M x M x M grids ( e.g.: 1030 for N=10, M=10 )

    DFT
    Kohn & Pople (1998, Nobel prize in chemistry)

    Total density of electrons is the same

    N non-interacting single-electron problems: Hi=ii where i=i (x,y,z) r 2 H= / 2 + Veff (r ) where Veff (r) is an effective potential Cost: NM3 for M x M x M grids (e.g.: 10 x103 for N=10, M=10 )

    How to do electronic structure calculations


    Initial assignment (geometry, total charge, spin conf., total moment) Place Gaussians on each atom as a basis set for an atomic wavefunction

    r r r 2 (r ) = Ck f k exp[ k (r Rk ) ]
    Solve N nonnon-interacting one-electron equations under effective potential self-consistently: Veff (r)= Vnucl+VH[(r)]+Vxc[(r)]

    NO
    Energy is converged?

    r [ / 2 + Veff (r )]i = i i
    2

    YES
    Calculate forces, (r), geometry

    NO YES Geometry
    Force is small? is optimized!

    Mn12: [Mn12O12(O2CCH3)16(H2O)4]
    T.Lis Acta Cryst. B36, 2042 (1980)

    1.5nm
    y x

    Mn4+ Mn3+

    Experimental data
    Single molecule: S4 symmetry 4 Mn4+ (3d3 ,S=3/2) ions in cube 8 Mn3+ (3d4 ,S=2) ions in outer crown Easy axis: z axis

    Total ground-state spin: S = 8 x 2 4 x 3/2 = 10

    Electronic structure & Magnetic anisotropy for isolated Mn12


    M. R. Pederson & S. N. Khanna, PRB 60, 9566 (1999)

    [Mn12O12(O2CH)16(H2O)4] All-electron density-functional theory (DFT)


    Mn (I) calculations using NRLMOL All ligands were included Total ground-state spin S=10 Spin density is localized on Mn ions Majority HOMO-LUMO gap=0.45 eV Minority HOMO-LUMO gap=2.08 eV Mn (III) Mn (II)
    NRLMOL:

    (2nd order) magnetic anisotropy barrier =55.7 K c.f. Expt: 55.6 K


    A.Fort et al., PRL (1998)

    M.R. Pederson & K.A. Jackson, PRB (1990); ibid, PRB (1991); K.A. Jackson & M.R. Pederson, PRB (1990); D. Porezag & M.R. Pederson, PRB (1996)

    How does a metal surface affect electronic structure and magnetic anisotropy of Mn12?
    gold surface

    Experiment
    Monolayer of Mn12 on gold surface
    L. Zobbi et al., Chem. Comm. 1640 (2005).

    ~20 nm
    S. Barraza-Lopez et al., Phys. Rev. B (2007).

    Theory
    Consider slab calculation: Mn12-S2gold surface

    short link

    Method & Model


    Spin polarized density-functional theory (DFT) Use Vienna ab-initio simulation package (VASP) PBE GGA for exchange-correlation potential Projector augmented-wave (PAW) pseudopotentials
    [Blchl, PRB (1994); Kresse & Joubert, PRB (1999)]

    - All-electron wavefunctions are available - To take into account spin-orbit coupling - Accuracy is improved in magnetic materials
    Au: s1 d10 Mn: 3p6 4s2 3d5 O: s2 p4 C: s2 p2 S: s2 p4

    Method & Model (continued)


    No chemical bonding between Au and Mn12 so two S atoms link Mn12 to Au All ligands are included in our simulations Mn12+linker+Au slab: Total 2886 valence electrons per unit cell Optimize Au slab and Mn12 separately to create a whole geometry

    Au(111) Au(111 ) slab


    Compute equilibrium lattice constant for bulk gold (4.175 ) With the calculated lattice constant, we construct Au monolayers Check convergence with # of k points and energy cutoff for plane waves To cover Mn12, at least 36 surface gold atoms per monolayer are needed Use six gold monolayers (36 x 6 = 216 gold atoms as a total) Relax gold slab (w/o molecule) until max forces are less than 0.01 eV/

    Isolated SS-terminated Mn12


    Mn12 with the lowermost H atoms replaced by S atoms, is adsorbed on Au Total magnetic moment of Sterminated Mn12 in ground state :18 18 B (c.f. ground state of Mn12: 20 B) By adding H below sulfur, the magnetic ground state goes back to 20 B
    Geometry 3
    H H

    Density of States: Geometry 2


    Spin polarization of sulfur evident from the density of states (DOS) HOMO-LUMO gap is created by sulfur pp-orbitals
    Sulfur p-orbitals hybridized with Mn d-, O pporbitals

    Building whole structure


    Unit cell 17.7 x 17.7 x 34.0 3 6 Au layers + S2 + Mn12 (Geo 2) + 10 vacuum Distance between closest H atoms in neighboring molecules: 3.35 . Interactions between molecules are weak. No further relaxation of the whole structure 4 k-points in 6x6x1 Au supercell Charge profile was computed; charge from Au slab has a tail going all the way to the lower section of magnetic molecule

    Energy levels around the Fermi level and charge transfer


    The location of the HOMOHOMOLUMO for the isolated Sterminated Mn12, relative to the Fermi energy of bulk Au, determines the direction of charge transfer, transfer from Au to the magnetic molecule Au Fermi level is above majority spin LUMO but below minority spin LUMO.

    Au Fermi level
    LUMO HOMO

    Density of states: states: Whole structure


    Upon adsorption, spin polarization of S atoms is lost

    Different scale

    Orbital broadening
    Mn12 molecular orbitals broaden upon adsorption Orbital broadening is much less than charging energy Weak coupling
    Isolated

    Isolated

    Charge transfer towards Mn12


    Determined via in-plane integration of the charge density for molecule with and without gold slab; 1.23 electrons; Au tail dominating.

    AB C

    Mn atoms in region C

    Calculated spin density


    Side view

    Spin density is localized on Mn


    Top view Red: up Blue: down

    Mn(I): inner, -2.588 B Mn(II): outer, 3.524 B Mn(III): outer, 3.543 B monoclinic unit cell 17.7 x 17.7 x 34.0 3

    Spatial change of magnetic moments


    From the plane-averaged magnetic moments along the z-direction, we find an increase of 2 B between the S-terminated Mn12 and the whole structure The whole structure has a magnetic moment of 20 B.
    Whole - 2

    2.0

    Barraza-Lopez, Avery and Park: PRB 76 224413 (2007)

    Magnetic Anisotropy in SMMs


    z y

    -e

    v
    Anisotropic

    Mn

    r r r r r B = v E = v ( )
    : Coulomb potential due to atomic nuclei and electrons

    e r r 1 r r r Spin-orbit VLS = S B = 2 2 S ( p ) coupling mc 2m c

    Magnetic anisotropy barrier for SS-terminated Mn12


    To compute magnetic anisotropy barrier, we consider spin-orbit coupling in DFT selfconsistently.
    H H

    Although total magnetic moment differs for Mn12 and Geo.2 (S-terminated Mn12), the MAB of ordinary Mn12 is the same as that of Geo. 2 Magnetic anisotropy barrier for Geo. 3 gets reduced by about 9%

    MAGNETIC ANISOTROPY BARRIER (K)

    Geometry 3

    Mn12 66.7

    Geo 2 66.9

    Geo 3 60.7
    S H

    Magnetic anisotropy barrier for whole structure


    Whole Geo 2 Geo Whole - 2 3 - Geo 2

    The spatial charge and magnetic moment distributes in a similar way for whole structure and Geo. 3. So [magneitc ansiotropy barrier (MAB) of Geo 3] = [MAB of whole structure] The magnetic anisotropy barrier for the whole structure is reduced by 9% of that for the isolated Mn12.

    2.0

    2.0 B

    MAGNETIC ANISOTROPY BARRIER (K)

    Mn12 66.7

    Geo 2 Geo 3 Whole 66.9 60.7 60.7

    Additional inclusion of electron electron-electron correlations: LSDA+U method


    Takes into account the orbital dependence of strong on-site correlations (in LSDA or in GGA), which is absent in standard DFT. Hubbard-like U term plays important role for localized d- or f-electrons. d- or f-orbitals are more localized and energy gap increases. Value of U term: depends on local environments, determined by experiment or standard DFT calculations by varying the occupancy of dor f-orbitals.

    V. I. Anisimov et al., PRB 44, 44 943 (1991) V. I. Anisimov et al., J. Phys.: Condens. Matter 9, 767 (1997)

    Effect of correlation: GGA+U


    On-site U=6 eV is considered for Mn d-orbitals Ordinary Mn12: HOMO levels are shifted down. HOMOLUMO gap greatly increases due to HOMO and LUMO that are from Mn d-orbitals. S-terminated Mn12 (Geo 2): HOMO, LUMO are from S porbitals so the gap does not change much. Direction of charge transfer does not change with U
    Barraza-Lopez, Avery and Park, J. Appl. Phys. (2008) Electronic level (eV)

    U=6*

    PBE GGA

    Mn12 HOMO Mn12 LUMO gap Geo 2 HOMO Geo 2 LUMO gap

    -6.13 -7.04 -5.08 -6.45 -4.78 -4.77 -4.84 -4.50

    1.35

    0.24

    -6.37 -6.66 -5.37 -6.07 -6.05 -5.51 -5.22 -4.84 0.32 0.15

    (*) Boukhvalov et al, PRB 75, 75 014419 (2007)

    Summary
    Modeled a monolayer of Mn12 adsorbed on a Au surface via a thiol group using DFT Electronic structure: broadening of molecular orbitals was small, weak coupling between Mn12 and a Au surface even with the short link Charge transfer from Au to Mn12 Total moment for whole structure back to 20 B Magnetic anisotropy barrier for whole structure is reduced by 9% compared to that for isolated Mn12 molecule Effect of on-site U on orbitals for isolated molecules
    Barraza-Lopez, Avery and Park: PRB 76 224413 (2007), JAP 103 07B907 (2008)

    Bulk gold & Au(111) slab


    Bulk gold: Equilibrium lattice constant = 4.175
    Exp: 4.078 , difference: 2.8%

    Check convergence with # of k points and energy cutoff for plane waves With calculated lattice constant, we vary # of Au layers and # of vertical vacuum layers Au surface energy saturates with 8 Au monolayers and 7 vacuum layers To cover Mn12, at least 36 surface gold atoms per monolayer are needed Use six gold monolayers (36 x 6 = 216 gold atoms) Relax gold slab (w/o molecule) until max forces are less than 0.01 eV/

    vacuum layer

    Projected density of states for Mn12 on Au slab

    Blue: Isolated Mn12 Red: Mn12 on Au slab

    3d

    3d

    Mn(I): inner, Mn(II), Mn(III): outer

    Projected density of states for Mn12 on Au slab

    3d
    Broadening of orbitals is much less than Coulomb charging energy: Weak coupling

    2p

    Mn(I): inner, Mn(II), Mn(III): outer

    Mn12 molecular orbitals eLUMO

    Au Fermi level 0.3 eV

    HOMO

    +2.0

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