Quantum Matter

1
Versatility of Magnetic Fields one mans
opinionan educated caveman
Quantum Matter Addressing our limited
understanding of strongly interacting quantum
systems Complex Fluids Studying nature as it
presents itself.messy Structure, Dynamics and
Function Exploiting Magnetic Resonance to
study organic moleculesto membranesto
cellsto brains Materials Science
Element-specific nuclear and electron spins to
understand specific element environments in
organometallics, catalysts, batteries Taking the
Magnets to the Neutrons. Taking the Magnets to
the X-rays. Bringing the Terahertz to the
Magnets. A proposed THz-to-IR Free
Electron Laser Light Source at the National
High Magnetic Field Laboratory
www.nap.edu
Greg Boebinger
2
Versatility of Magnetic Fields one mans opinion
www.nap.edu
Quantum Matter Putting metals on
teeter-totters Scotch-tape-induced
relativity Materials research Saving lives
for more than 2000 years
3
State-of-the-Art Fermi Surface Studies quantum
oscillations in pulsed magnetic fields
Intense magnetic fields exponentially amplify
quantum oscillations.
dHvA in YBCO Ortho-II Doiron-Leyraud, et al
Nature 450 533 (2007)
Pulsed magnetic fields have enabled quantum
oscillation experiments in ? high-temperature
superconductors ? heavily
disordered metals and alloy series ? compounds
with heavy electron masses, and ? at
temperatures up to 100 K
Quantum oscillationstheyre not just for ground
states anymore
4
State-of-the-Art Fermi Surface Studies Tilting
low-dimensional metallic samples in a constant
magnetic field
Hussey et al, Nature (2003) Full
Three-Dimensional Mapping of the Fermi Surface
in a High-Tc Superconductor Tl2Ba2CuO6d (Tc
20K)
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Quantum Oscillations in YBCO-Ortho II
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Low-temperature Hall Number Evidencing Fermi
Surface Reconstruction at Optimum Doping ?
First observed in Bi-2201
(Bi2Sr2-xLaxCuO6d)
The same sharp peak in doping dependence of the
Hall number at optimum doping in both BSLCO and
LSCO
Balakirev, et al. Nature 424, 912 (2003)
Balakirev, et al. cond-mat arXiv 0710.4612
7
Natures (and Sciences) latest Low-Dimensional
Electron System
In 45T Magnetic Fields
Energy
Novel Series of Quantum Hall Plateaus and
Room-Temperature Quantum Hall Plateau
Momentum
Single-layer Graphene Linear dispersion
Tune density with Gate Voltage
Novoselov, et al. Science (2004) Zhang et
al. Nature (2005) Novoselov, et al. Nature (2005)
8
Spin Control Room Temperature Qubits
K3NbO8 doped
with Cr5 with a 1/2 local spin
Minimal spin interactions with
the local environment
Rabi oscillations (figure) observed up
to 290K At 4K, T2 10 µs and 20MHz Rabi
frequency yields a single qubit figure of merit
500 for this transition metal oxide system.
S. Nellutla, K.-Y. Choi, M. Pati, J. van Tol, I.
Chiorescu and N. S. Dalal, Physical
Review Letters 99, 137601 (2007)
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2500 Years of Materials Research on
BaCuSi2O6 Chinese Terracotta Warriors (479-221 BC)
Calcite - CaCO3 Bone White - Ca5(CO3)2(OH)2 White
Lead 2Pb(CO3)2Pb(OH)2
Soot - carbon black
Han Purple - BaCuSi2O6
Han Purple - BaCuSi2O6
Terracotta Army to protect the emperor in the
afterlifeinstead of the real army
Cinnabar - HgS Hematite - Fe2O3 Red Lead Pb3O4
Malachite Cu2CO3(OH)2
Han Blue BaCuSi4O10
man-made pigments
J. Zuo et al., J. Raman Spectrosc. 34, 121
(2003) H. Langhals D. Bathelt, Angew. Chem.
Int. Ed. 42, 5676 (2003)
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Materials Research Saving Lives for more than
2000 Years
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Versatility of Magnetic Fields one mans opinion
Quantum Matter Putting metals on
teeter-totters Scotch-tape-induced
relativity Materials research Saving lives
for more than 2000 years Complex Fluids
Weighing molecules that weigh the same
Petroleum goop and pee Little tiny
holes in little tiny viruses Insect spit and
worm sex
12
Ion Cyclotron Resonance Putting Molecules Into
Orbit
With a 14 T high-homogeneity wide-bore magnet,
100 part-per-billion mass resolution and
accuracy petroleum and metabolic compounds
gt100,000 resolved compositionally-distinct
organic molecules in a single petroleum sample

• Petroleomics
• Fingerprint of each oil reservoir
• Sulfur-containing compounds
• Fresh- and salt-water solubility
• Analysis of pipeline clogging
• Refinement of sour crudes

• Possible future applications
• Antibodies in cerebrospinal fluid, bloodstream
  or urine
• Amyloid mixtures, plaque deposits
• Nutritional components in food and food
  processing assurance
• Arson accelerants and explosives residue

13
Fighting Viruses Plugging the RNA channels
Combining Ion Cyclotron Resonance and Nuclear
Magnetic Resonance
Structure of Macro-bio-assemblies
Hydrogen/Deuterium Exchange Rate reveals
which side of the RNA channel is on the virus
exterior
gt 100 h-1 FAST 10 h-1 - 100 h-1 1 h-1 - 10 h-1
0.1 h-1 - 1 h-1 lt 0.1 h-1 SLOW
RNA Channel (side view) mass increase rates
when fully exposed to deuterium
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NMR Spectrum From a Single Animal

• Can accurately spray venom up to 40 cm
• Temporarily blinds potential predators
• Monoterpene dialdehyde called anisomorphal

• Dissolve secretion in 10 ?L D2O
• No purification10nL sample (0.1mm)3
• Collect NMR 10 min after secretion

YBCO rf coil
15
Isomeric Heterogeneity among individualsor as a
function of time for the same individual
Anisomorphal has 3 stereocenters 4 possible
diastereomers
Peru isomer
16
Versatility of Magnetic Fields one mans opinion
Quantum Matter Putting metals on
teeter-totters Scotch-tape-induced
relativity Materials research Saving lives
for more than 2000 years Complex Fluids
Weighing molecules that weigh the same
Petroleum goop and people pee Little
tiny holes in little tiny viruses Insect spit
and worm sex Structure, Dynamics and Function
Advanced MRI of mouse brains and
fatheads Watching water diffuse
17
MRI goes High-Defand soon in Technicolor !
900MHz / 105 mm Ultra-Wide Bore NMR/MRI Magnet
Contrast agents can be synthesized with different
metals and chelating groups to create tunable
contrast and multiple color imaging.
in vivo MRI of the Mouse Brain using the 21T MRI
magnet
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Magnetic Quantum Dots for Live Cell Tracking
Living stem
cells, labeled with bio-compatible Gadolinium
nanoparticles tracked in vivo using
Magnetic Resonance Imaging in a mouse brain
as they respond to brain damage resulting from
hypoxia.
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Quantitative MR Imaging
MRI can go beyond pretty pictures to make an
even bigger impact in biochemistry, cell
biology, physiology, neuroscience, and related
fields.
Mouse Brain Atlas Defines normal by averaging
data from many brains Highlights regions of
individual brain variability due to
disease or resulting from genetic
manipulation
Measuring water diffusion with MRI provides
needed structural information about tissue
connectivity. For example, nerve membranes
restrict the diffusion of water and allow the
visualization of nerve fiber tracts that connect
functional areas in the nervous system.
20
Versatility of Magnetic Fields one mans opinion
Quantum Matter Putting metals on
teeter-totters Scotch-tape-induced
relativity Materials research Saving lives
for more than 2000 years Complex Fluids
Weighing molecules that weigh the same
Petroleum goop and people pee Little
tiny holes in little tiny viruses Insect spit
and worm sex Structure, Dynamics and Function
Advanced MRI of mouse brains and
fatheads Watching water diffuse Materials
Research Nucular Resonance across the
entire periodic table Finding the unpaired
electron spin Better living through magnets
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Oxygen-17 Nuclear Magnetic Resonance
Spectroscopy a new tool for studying biological
membranes
K ion

Our entire nervous system is dependent upon the
proper function of ion channels,
pores in cell
membranes that are able to transport ions, such
as potassium and sodium,
in and out of the cell.
Because 17O is a quadrupolar
nucleus, it is a very sensitive indicator of the
electric fields of nearby ions.
At 21.1 teslas in the 900MHz magnet

we can detect
NMR line shifts due to the electric
fields
of
potassium ions at particular sites

along the
ion channel
Ion Channel
22
Quadrupolar Nuclei the REST of the Periodic
Table
Most nuclei are quadrupolar spins (Sgt1/2) High
magnetic fields are essential for NMR research
on quadrupolar nuclei
Materials Physics
I 1 2H, 6Li, 14N I 3/2 7Li, 11B,
23Na, 69,71Ga, 87Rb I 5/2 17O, 25Mg,27Al,
47Ti, 67Zn
Elements with Only I 1/2 nuclear
spins Quadrupolar nuclei
(i.e. I gt 1/2 )

• Catalysts
• chemistry is only skin deep
• Porous materials
• cell membranes to zeolites
• Batteries and fuel cells
• wheres my Lithium ?

23
Electron Spin Resonance to Probe Organometallics
High-frequency ESR and magnetic-field dependent
spectroscopy required to measure the g-tensor for
the unpaired electron spin, i.e. to understand
the environment of the metallic ion
Iron is important in bio-inorganic chemistry,
appearing in many metallo-proteins (proteins
that function due to the
incorporation of a metallic ion). Despite being
paramagnetic, the Fe(II) oxidation state of
iron is very difficult to detect due to a
very large zero-field splitting (12 cm-1
in the ground spin state).
MagLab 25T / 20ppm
In 2012 36T / 1 ppm
9 GHz common lab spectrometer
94 GHz Highest commercially available
spectrometer
Electron Spin Resonances of Iron(II) in
bis(2,2-bi-2-thiazoline) bis(isothiocyanato)
iron(II)
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Multifrequency Electron Spin Resonance
Structure and Dynamics of Macromolecules

ESR spectra of the T4 Lysozyme
Spin-labeled using MTSSL spin-label on site 131
(red at left)

• T4 Lysozyme
• damages bacterial cell walls
• abundant in tears, saliva, mucus
• helps white blood cells engulf bacteria
• and a model system for spin-labeling
• (Mchaourab, et al. (1996) Biochemistry 35 7692)

Selectively probe multiple sites via spin
labeling with unpair spin at many
different residues Probe dynamics at each site
using a range of frequencies (ie magnetic
fields)

Jack Freed, Cornell
25
Finding Unpaired Electrons in Palladium
A frontier of modern chemistry the
understanding of catalysis on a molecular
level.
Paddle-wheel s ½ complex Pd2 (DAniF)4 PF6
A wide variety of palladium molecules,
including the paddle wheel compound above, are
being studied for use as new catalysts.
Catalysts find extensive industrial use for their
ability to nucleate and accelerate chemical
reactions. Although X-rays can determine
the location of all the atoms in a molecule,
catalysis depends instead on the location of the
electrons, in particular the location of the
unpaired (hence chemically active) electron.
Electron paramagnetic resonance (EPR), the
flipping of an electrons intrinsic magnetic
field, is the technique of choice for settling
whether the unpaired electron is spread over the
central metallic core or the ligands, the
peripheral parts of the molecule.
Figure The High frequency EPR spectra of Pd2
(DAniF)4 Note the increased resolving power
of higher magnetic fields, which requires higher
frequency spectroscopy.
26
Energy Transfer Photosynthesis and Solar Cells
Photon energy ? Chemical energy CO2 ? O2 (for
green plants)
P ?P?P e-
hn
3P
P
e-
Fe
Optical excitation, charge separation, and charge
transport over the membrane involves many
intermediate states Most of the intermediate
states are paramagnetic. High-frequency (and
hence High-Magnetic-Field) Electron
Paramagnetic Resonance probes these states
27
Actinide Chemistry is Complicated
(and Environmentally Important)

• Some gross condensed phase
• leaching behavior
• Improperly disposed radioactive waste an
  uncontrolled and ongoing chemistry experiment
• What is there ?
• Where is there ?
• How much longer before there changes ?
• Environmental disposition is ultimately
  determined by
• structure of the radioactive complex
• and the presence of solvents
• Solid vs solution partitioning
• varies with mix of sample
• varies with local environment
• varies dramatically with pH

55 gallon drumat 55 years of age
28
Materials-Limited Superconducting Magnet
Applications
Materials Research Saving lives for the next
2000 years
High Tc magnets should greatly shrink the
proton source replacing X-ray radiation
therapy in existing hospital space
The ITER fusion reactor will use 1B of
Niobium-based 13 T superconducting
magnets .but present Nb3Sn conductor is too
lossy for required sub-second magnet pulsing
29
Unrealized Opportunities for increased
Scientific Impact of High Magnetic Field Research
PARTNER with NATIONAL LABORATORIES to marry
Magnetic Fields with other Scientific
Probes Neutrons, X-rays, Infrared, and
Terahertz
www.nap.edu
From scientific and budgetary considerations
1. Take the magnets to the
Neutrons at the
Spallation Neutron Source 2. Take the
magnets to the
X-rays at the Advanced Photon Source 3.
But bring the Infrared and Terahertz to the
Magnets THz-IR Free Electron
Laser at the National High Magnetic
Field Laboratory
Greg Boebinger, MagLab
30
ZEEMANS Ze Extreme Magnetic Neutron
Spectrometer Collaboration with Johns Hopkins and
the Spallation Neutron Source (Design Proposal is
Fundedsimilar proposal submitted with
Hahn-Meitner Institute)
SERIES CONNECTED HYBRID TECHNOLOGY x3 lower
power than resistive magnets 32T, 32mm
bore, 10MW
Down Bore Neutron Beam
A fourth branch of the MagLab at a 32T SNS
beamline ?
/- 20 Degree Scattering Angle
Hard condensed matter High Tc
Superconductivity Vortex matter Model
magnet systems (1D, 2D, and frustrated 3D)
Multi-ferroics Charge, lattice and spin
correlations
Nano-scale Materials Sciences Magnetic
multilayersfor magnetic field sensors
Metallurgical nano-structure and
macro-properties Phase-separation in
correlated electron materials
New instruments for studying the neutron and
x-ray scattering properties of materials in high
magnetic fields should be developed in the United
States.
COHMAG,
p.5
31
B
X-rays and 30 Tesla Magnets Proposed
Collaboration with MIT and Advanced Photon Source
SERIES CONNECTED HYBRID TECHNOLOGY Lower
power (10MW) than resistive magnets 30
Teslas in a 32mm sample bore Down-bore
magnet (conical bore magnet) Split magnet
(gap at magnets equatorial plane)
APS
25 T Split Magnet
30 T Conical Magnet
30 T Conical Magnet
Proposed location for High Magnetic Field
Beamline
25 T Split Magnet
32
Science Hidden by our Blind-Spot in the Terahertz
Regime
Resolving Biofunctional Isomers (sugar coating
helps antibodies recognize antigens)
Complete Vibrational Spectra of Macromolecules
(backbone bending to individual bonds)

Actinide Chemistry (bond-specific multi-photon
infra-red dissociation)
Molecular Magnets (atomic nitrogen qubit in C60
cage)

Vibrational Mode Coupling (two-dimensional
pump-probe infra-red spectroscopy)
Understanding Catalysis at the Molecular
Level (palladium paddle-wheel catalyst)
Harvesting Solar Energy (energy transfer on the
nanoscale)
Imaging the warm bits
33
Conceptual Design Completed
10m x 40m footprint
34
A Fourth Generation Terahertz-to-Infrared Free
Electron Laser at the MagLabs National User
Facility
The 2M Conceptual Design is Completed
Using Existing JLab Designs to Minimize
Risk and Cost and Time to First Light
25-30M Cost and Commission BigLight FEL 10-15M
FEL Specific Infrastructure 20M FEL
Building
If funded mid-2009, if building ready by
mid-2010, then first light in 2012
35
Cyclotron energy in semiconductors (m 0.05 is
shown)
.and condensed matter physics
Lattice Molecular Vibrations
Collective Modes in Correlated Electron Systems
Cuprate Pseudogaps
Superconducting Bandgaps
Frequency ( GHz )
Magnetic Excitations
m 1 Cyclotron energy g 2 Zeeman energy

Magnetic Field ( T )
36
Versatility of Magnetic Fields Horrendous
Opportunities and Appalling Advantages
Quantum Matter Putting metals on
teeter-totters Scotch-tape-induced
relativity Terracotta army Complex Fluids
Weighing molecules that weigh the same
Petroleum goop and pee Little tiny holes
in little tiny viruses Insect Spit and Worm
Sex Structure, Dynamics and Function
Advanced MRI of mouse brains and
fatheads Watching water diffuse Materials
Research Nucular Resonance across the
entire periodic table Finding the unpaired
electron spin
37
Terahertz-to-Infrared Free Electron Laser
National User Facility
38
Broadband Terahertz Source (at Bending Magnet)
39
Broadband Terahertz Source (at Bending Magnet)