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HIGHHIGH--PRESSURE SYNCHROTRON PRESSURE SYNCHROTRON INFRARED SPECTROSCOPY:INFRARED SPECTROSCOPY:New Light on Materials under Extreme New Light on Materials under Extreme ConditionsConditions

Russell J. HemleyRussell J. Hemley

Geophysical Laboratory Geophysical Laboratory Carnegie InstitutionCarnegie InstitutionWashington, DCWashington, DC


ACKNOWLEDGEMENTS

CollaboratorsCARNEGIE INSTITUTIONCARNEGIE INSTITUTIONZhenxian LiuHo-kwang Mao Daniel HausermannJinghzu Hu Quanzhong Guo Yingwei Fei Sarah StewartViktor Struzhkin M. SomayazuluJinfu Shu Eugene Gregoryanz Wesley Huntress Yue MengJian Xu

OTHER INSTITUTIONSLarry Carr (NSLS)Dennis Klug (NRC)Mikhail Eremets (Mainz)Alexander Goncharov (LLNL)Wendy Mao (Chicago)Dudley Herschbach (Harvard)Henry Scott (Indiana SB)James Badro (Paris)T. Lin (Scripps)Michael Kruger (UMKC)Lisa Miller (NSLS)Chi-chang Kao (NSLS)Anurag Sharma (RPI)Yusheng Zhao (LANL)Joe Zaug (LLNL)

Financial SupportDOE/BES Carnegie InstitutionNSF (COMPRES)


OUTLINE

I. Introduction STATIC HIGH-PRESSURE SCIENCE UNIQUE ADVANTAGES OF SYNCHROTRON INFRARED

II. Highlights: A Decade of New Findings SELECTED APPLICATIONS:

Physics, Chemistry, Materials Science, Earth and Planetary Science, Biology and Soft Matter

III. New Opportunities and ChallengesSELECTED GRAND CHALLENGES A NEW OF HIGH-PRESSURE DEVICESPOSSIBLITIES FOR NSLS-II

Synchrotron infrared and high pressureSynchrotron infrared and high pressure-- an extraordinary matchan extraordinary match

Synchrotron IR/xSynchrotron IR/x--ray probesray probes-- unique capabilities of the NSLS

Full integration ofFull integration of techniques techniques -- future facilities

THEMESTHEMES

future facilities


10-32

10-24

10-16

10-8

1

108

1016

1024

1032

10-8

10-6

10-4

10-2

1

102

104

106

108

RANGE OF PRESSURE IN THE UNIVERSERANGE OF PRESSURE IN THE UNIVERSEPr

essu

re (A

tmos

pher

es)

Pres

sure

(Atm

osph

eres

)

Hydrogen gas in intergalactic space

Interplanetary space

Center of neutron star

Atmosphere at 300 miles

Center of Jupiter

Center of white dwarf

Center of Sun Deepest ocean

Best mechanical pump vacuum

Water vapor at triple point

Center ofthe Earth

Atmospheric pressure (sea level)


ADVANCES IN STATIC HIGH PRESSUREADVANCES IN STATIC HIGH PRESSURE

PRESSURE UNITS

103 atm ≈ kbar106 atm ≈ Mbar10 kbar = 1 GPa1 Mbar = 100 GPa

1 Gigapascal = 109 N/m2

13524

335363

P (GPa)


Free Energy Changes and Chemical BondingFree Energy Changes and Chemical Bonding

• P-V work can exceed binding energies

• Dramatic changes in bondingand electronic states

• Stored energy in metastablephases

[Hemley and Ashcroft, Physics Today 51, 26 (1998)]


2.0

1.5

1.0

0.5

0.0

-Log(

I/I

0)

160140120100806040

Energy (keV)

2 x 2.5 mmdiamonds

Radial

4 6 8 10 12 14 16 Energy(k V)

Axial

2 mm Be

-Log(I/Io)

2.0

1.5

1.0

0.5

0.0

diamonds

beryllium

REE L

TransE Kα

α

Supportingseats

20 0m m

HIGHHIGH--PRESSURE TECHNOLOGYPRESSURE TECHNOLOGYPlethora of New InstrumentsPlethora of New Instruments


50 GPa ~200 µm 300 GPa <10 µm

P dd

Synchrotron Infrared Spectroscopy and High PressureSynchrotron Infrared Spectroscopy and High Pressure

10000 1000 100 10 1108

109

1010

1011

1012

1013

1014

1015

1016

1017

1018

1019

2000K Black Body

U4IR

NSLS U2B Mk.2 40 mrads hor40 mrads vert.

NSLS U2B 12 mrads hor8 mrads vert.

Pho

tons

/sec

/0.1

%bw

/mm

2 sr

Wavelength (microns)

NInfrared Brightness

U4IR: 1990-1992• First megabar synchrotron IR measurementsU2B: 1992-1998• PRT with NSLS, Northrup Grumman• Nicolet 750; custom built microscopesU2A: 1998-• PRT with NSLS• Integrated optical/IR spectroscopy facilityU2A: 2004-• Improved beam delivery• Far-IR enhancement

High-Pressure Beam lines

IR

X-RAY


U2A Beamline Upgrade: IMPROVED FAR-IR AND BEAM DELIVERY

M2M1

Detector

VacuumBench

N2 purgedBruker IRscope II

Diamond cell in the cryostat

Ø10mmdiamondwindow

Vacuum box

Vacuumpipe

VacuumMicroscope

MCT DetectorBolometer

DACMCT Detector

KBr window

FS

FSN2 purged Low-T

Far/Mid-IR MICROSCOPE

MCT 1

MCT 2

Bolometer

Laser FS Microscope 2

Microscope 1

Microscope 3

Visible spectrograph

CCD detector

notch filters

• Near IR through far IR spectral range

• Reflectivity and absorptionmeasurements

• Low-temperature measurements• Mapping of the samples• In situ Raman and fluorescence

measurements• Diamond lens• Small diamonds

NSLSVUV

Bruker IFS66v/sFTIR Spectrometer

Ø10mmdiamondwindow

eyepiece

Diamond lens


1. Condensed Matter PhysicsA WEALTH OF FINDINGS:A WEALTH OF FINDINGS:

- HYDROGEN AT MEGABAR PRESSURES

Pressure (GPa)

100 120 140 160 180 200

Tem

pera

ture

(K)

0

50

100

150

200

250

III

II

ITriple point

p-H2

n-H2p-H2Lorenzana et al.

ANOMAlOUSCHARGE TRANSFER STATE

[Hemley et al., Nature 369, 384 (1994)]

UNEXPECTED PHASE DIAGRAM

NO “MOLECULAR”METALLIZATION (to 230 GPa)[Hemley et al., Phys. Rev. Lett. 76,

1667 (1996); Chen et al. Phys. Rev. Lett. 76, 1667 (1996) ]

IR Absorption

Wavenumbers (cm-1)

4300 4400 4500 4600 4700

Abs

orba

nce

181166156

14812369

P(GPa)

85 K

H2

151

Infrared Absorption

0.5

[Mazin et al., Phys. Rev. Lett. 78, 1066 (1997);Goncharov et al., ibid. 75, 2514 (1996); Lorenzana et al., ibid., 63, 2080 (1989)]

→


[Goncharov et al., Proc. Nat. Acad. Sci. 98, 14234 (2001)]

[Kohanoff et al., Phys. Rev. Lett. 83, 4097 (1999)]

Wavenumber (cm-1)

4600 4800 5000 6000 6200 6400

Abs

orba

nce

0.05

4000 4200 4400

0.5

VibronCombination bands

248 GPa

205 GPa20 K

H2140 K

• Molecules stable to 300 GPa in solid• Constraints on the crystal structure


MultimegabarMultimegabar VibrationalVibrational SpectroscopySpectroscopy



[Chen et al. Phys. Rev. B64, 20040 (2002)]

600 700 800 900 10001100100 200 300 400 500 600

1 atm

Mid-IR

pressure released

4.0

2.6

2.01.71.10.60.4

0.2

1 atmAbso

rban

ce (a

rb. u

nit)

Far-IRHfW2O8

1 atm

4.0

2.62.01.71.10.60.4

0.2 GPa

Wavenumber (cm-1)Pressure-induced amorphization of HfW2O8

[Struzhkin et al., Phys. Rev. B 62, 3895 (2000)]

- NOVEL TRANSFORMATIONS

Pressure (GPa)

0 5 10 15 20 25

ω/ω

0-1

0.0

0.1

0.2

0.3

0.4

Col 1 vs Col 2 2-Magnon Raman, 300 K RegrCol 30 vs Col 31 2-Magnon IR, 300 K RegrCol 30 vs Col 34

Sr2CuCl2O2 magnon excitations IR, NaCl medium

Wavenumber (cm-1)

4000 6000

Abs

orba

nce

2-M 4-M

Inte

nsity

(a. u

.)

2.2

3.9

5.4

7.0

9.1P, GPa

- MAGNON EXCITATIONS

- INFRARED EXCITATIONS IN HIGH-Tc SUPERCONDUCTORS

[Struzhkin et al. J. Phys. Condens. Matter, in press]


HH22OO--ICE UNDER PRESSURE ICE UNDER PRESSURE 200

150

100

50

0

Pre

ssur

e (G

Pa)

181614121086

Volume (cm3

/ mol)

Ice VI

Water

Ice VII

Volume (cm3/mol)

Pres

sure

(GPa

)

Compression of HCompression of H22OO(300 K)(300 K)

200

0

50

100

150

6 8 10 12 14 16 18

Ice VIWater

Ice X

Ice VII

[Hemley and Mao, J. Phys . Condens , Matter 49, 11157 (1998)]

• bcc-like oxygen for ice VII and X• No other major phase transitions to at least 210 GPa

[Goncharov et al., Science273, 218 (1996)]

HIGH PRESSURE SPECTRAHIGH PRESSURE SPECTRASynchrotron Infrared Reflectivity

T1u T1u

• Non-molecular ice identified by IR reflectivity above 60 GPa• X-ray Confirms spectroscopic data: bcc-based structure

2. ChemistryA WEALTH OF FINDINGS:A WEALTH OF FINDINGS:


A WEALTH OF FINDINGS:A WEALTH OF FINDINGS:2. Chemistry- ANOMALOUS

TRANSITIONS IN ICE VIII

100 200 300 400 500

6.514.71

2.08

0.14

1.48

2.83

4.12

6.18

7.98 GPa

D2O 85 K

Abs

orba

nce

(arb

. uni

t)

Wavenumber (cm-1)0 2 4 6 8

150

200

250

300

350

400

450D2O 85K

decompression

compression

Wav

enum

ber (

cm-1)

Pressure (GPa)

?

Pressure dependence of IR translational and rotational mode frequencies in D2O No transition

[Klug et al., Phys. Rev. Lett., submitted]


A WEALTH OF FINDINGS:A WEALTH OF FINDINGS:2. Chemistry

- NOVEL MOLECULAR PHASES

Raman Shift (cm-1)

2350 2400 2450200 400 600

Ram

an In

tens

ity (

arb.

uni

ts)

N2

ζ

ι

θ

Wavenumber (cm-1)

2400 2450

Ab

sorb

ance

θ

ι

ζ

0.2

2400 2420

θ

x10•• Quenchable to 300 KQuenchable to 300 K• Polynitrogen: e.g., N5

+ N5-

IR

- VAN DER WAALS COMPOUNDS

[Loubeyre et al. (1994); Datchi et al. (1997);Hemley (2000); Ulivi et al. (2001)]


X-ray

• NO+-NO3-: an unusual ionic

phase probed by far-IR and x-ray

A WEALTH OF FINDINGS:A WEALTH OF FINDINGS:2. Chemistry

- NOVEL MOLECULAR PHASES

NO+-NO3-β-N2O

→

Far-IR

[Somayazuluet al., Phys. Rev. Lett. 87, 135504 (2001); Songet al. 119,2232 (2003)]


- VIBRATIONAL PROPERTIES(Transition mechanisms and thermodynamic properties)

- INSULATOR-METAL TRANSITIONS - MICROSPECTROSCOPY OF INCLUSIONS- DENSE SILICATES IN THE MANTLE

0 1 0 0 2 0 0 3 0 0 4 0 0

1 0 0 0

3 0 0 0

5 0 0 0

7 0 0 0

9 0 0 0

T h e o r y

S h o c k W a v e

S t a t i cδ

εγ

α

Tem

pera

ture

(K)

P r e s s u r e ( G P a )

3. Earth and Planetary ScienceA WEALTH OF FINDINGS:A WEALTH OF FINDINGS:

Phase D

Superhydrous B

Lawsonite

Phase B Phase E

Phase A

HYDROUS PHASES IN THE DEEP MANTLE:HYDROUS PHASES IN THE DEEP MANTLE:Hydrogen Incorporation in Dense Silicates

In SituIn Situ Measurements:Measurements:MULTIPLE CRYSTALSMULTIPLE CRYSTALS

200 µmDisplacive transformation in cummingtonite

[Yang et al., Am. Mineral. 83, 288 (1998)]



High-Pressure Behavior of K1.54Mg1.93Si1.89O7H1.04

• H disordering above ~15 GPa• Crystalline-crystalline transformation

3000 3500

ν3 ν2

ν1powder

8.0

20.5

16.7

12.1

4.9 GPa

1 atmsingle crystal

Abs

orba

nce

(arb

. uni

t)

Wavenumber (cm-1)1.6 1.8 2.0 2.2 2.4 2.6 2.8

Å

(112

)

(008

)

(204

) (114

)

(113

)

(111

) (110

)

(104

)

Imte

nsity

(arb

. uni

t)

Ar

Ar

20.5

16.7

12.1

8.0

4.9 GPa1atm

d-spacing ( )

0 5 10 15 20 25 30

0.86

0.88

0.90

0.92

0.94

0.96

0.98

1.00

c/c0

a/a0

V/V0

Com

pressibility

P (GPa)

IRIR XX--rayray

[Liu et al. J. Phys.: Condens. Matter 14, 1064 (2003)]



• Hydrocarbon stability tomegabar pressure300 K compression

• Consistent with powderand single-crystal diffraction

• New physics (H-rich alloy)?

~ 2000 K~10 GPa

~ 5000 K ~300 GPa

~ 7000 K ~800 GPa

~ 70 K~0.1 MPa

Wavenumber (cm-1)

1000 2000 3000 4000 5000

Abso

rban

ce

127 GPa

107

87

69

52

ν3

0.2

ν4 Methane 300 K

IR AbsorptionIR Absorption

- PLANETARY GASES AND ICES

[Badro et al., to be published]


100 200 3000

1

2

3

4

5

6

7

92.5

56.6 cm-1

HEME C-12

sample size: d=810 µm t=280 µmscan: 20 minutes

Mylar6

Mylar23

Abs

orpt

ion

coef

ficie

nt (m

m-1)

Wavenumber (cm-1)

HEME DOMINGHEME DOMING--MODEMODE

0 2 4 6 850

60

70

decrease P

HEME C-12

P (kbar)

increase P

Wav

enum

ber (

cm-1)

• Doming mode found at 57 cm-1

• Far-IR at high pressure

[Klug et al., Proc. Nat. Acad. Sci. 99, 12526 (2002)]

4. Biology and Soft Matter

- BIOMOLECULE VIBRATIONAL DYNAMICS

- BIOCHEMICAL REACTIONS IN HYDROTHERMA FLUIDS

- LIFE IN EXTREME ENVIRONMENTS(>1600 MPa)

[Sharma et al., Science 295, 1514 (2002)]

A WEALTH OF FINDINGS:A WEALTH OF FINDINGS:


- SUPERHARD MATERIALS- HYDROGEN STORAGE MATERIALS

5. Materials Science and TechnologyA WEALTH OF FINDINGS:A WEALTH OF FINDINGS:

[Zhao et al., J. Mat. Sci., in press]

[Goncharov et al., Phys. Rev. Lett. 85, 1262 (2000); Eremets et al. Nature 411, 170 (2001)]NITROGEN DISSOCIATION

Novel H2-H2O structure II clathrateStable at ambient pressure to 145 K5.3 % hydrogen (4.5 % DOE 2005 target)

- HIGH ENERGY DENSITY MATERIALS

[W. Mao et al. Science 297, 2247 (2002)]

Wavenumber (cm-1)

2400 2450 2500

Abso

rban

ce

60 GPa

170 GPa

160 GPa

151 GPa

140 GPa

134 GPa

115 GPa

97 GPa

80 GPa

N2 0.1

SEMICONDUCTING BEHAVIOR


OPPORTUNITIES AND CHALLENGESOPPORTUNITIES AND CHALLENGES

• Higher pressures and temperatures- physics/chemistry/astrophysics/planetary science

• Higher precision/acccuracy/sensitivity- all pressure ranges

• Broader wavelength range- far-IR, THz

• Time resolution- transition kinetics to chemical dynamics

• Integration of techniques- diffraction, inelastic scattering, imaging

• New generation of instrumentation- large volume, smart anvil cell designs


4100 4150 4200 4250 43000

100

200

300

400

500

Inte

nsity

(ar

b. u

nits

)

300 K

570 K

755 K

923 K

1114 K

Raman shift (cm )−1

• Liquid ground state? • High-Tc superconductor?• Higher P-T needed• Infrared combined with x-ray inelastic

scattering phonons/electrons

Raman72 GPa

FLUID

SOLID

[Gregoryanz et al., Phys. Rev. Lett. 90, 175701 (2003)]

Pressure (GPa)

0 50 100 150 200 250 300 350

Tem

pera

ture

(K)

0

500

1000

1500

2000

2500

3000

SOLID

LIQUID LIQUID (METAL)

I

II

III

Shock wave, Weir et al.

Theory (Scandolo et al.)

Datchi et al.

Our data

Hydrogen

Kechin extrapolation

Grand Challenge of Hydrogen at Extreme P-T

FLUID

OPPORTUNITIES AND CHALLENGES:OPPORTUNITIES AND CHALLENGES:

?


OPPORTUNITIES AND CHALLENGES:OPPORTUNITIES AND CHALLENGES:Electronic Structure, Bonding, Synthesis of Novel Materials

[Struzhkin et al. (2002)]

[Gao et al. (1994)]

HgBa2Ca2Cu3O8+d

- HIGHEST TEMPERATURE SUPERCONDUCTIVITY Tc = 164 K at 30 GPa

- EXCITONIC INSULATOR STATES?

0 1 2 3

1,544

1,546

Temperature, K

0,936

0,938

155 GPa

141 GPa

ElectricalResistivity to

27 mKand 160 GPa

Xe

[Eremets et al. (2000)]

-NOVEL SUPERCONDUCTORS(e.g., 23 elements; O, S, B, Fe, Li)

• Integrated studies to >300 GPa and to millikelvin temperatures

• Far-IR to optical range • Combined with x-ray inelastic

scattering phonons/electrons• Recovery to ambient


OPPORTUNITIES AND CHALLENGES:OPPORTUNITIES AND CHALLENGES:Spectroscopy of Earth Materials at Extreme P-T

- NATURE OF THE CORE FROM IN SITU OPTICAL STUDIES- CHEMICAL REACTIONS IN THE DEEP EARTH- HYDROCARBON STABILITY AND ENERGY RESOURCES- IN SITU HIGH P-T STUDIES OF

PLANETARY GASES AND ICES

~ 2000 K~10 GPa

~ 5000 K ~300 GPa

~ 7000 K ~800 GPa

~ 70 K~0.1 MPa


OPPORTUNITIES AND CHALLENGES:OPPORTUNITIES AND CHALLENGES:Life in Extreme Environments and Origin of Life

• IR/optical/x-ray imaging with P-T-t

• Single cells under stress

• “Test-tube” study of microbial evolution and adaptation

• Combined with otherprobes in new instrumentation

- BIOCHEMICAL REACTIONS - HIGH-PRESSURE MICROBIOLOGY

[Sharma et al., Science 295, 1514 (2002)]


OPPORTUNITIES AND CHALLENGES:OPPORTUNITIES AND CHALLENGES:

Growth of Diamond Anvils by Homoepitaxial Chemical Vapor Deposition

Towards TPa Pressures with Large Volume Anvil Cells

0.025 ct 0.25 ct 2.5 ct 25 ct

7.5mm 16.2mm3.5mm1.7mm

CVD homoepitaxial growth

[Yan et al. PNAS 99, 12523 (2002)]

Diamond Growing in a Plasma Reactor

GOALS:

• Higher pressures (1 TPaor 10 Mbar) and temperatures (>1 eV)

• Larger sample volumes needed (e.g., diffraction limited far-IR)

• Accuracy/precision compromised

• Applications of several simultaneous probes limited

•• 2.45 mm high• 0.28 carats• 0.45 mm seed• Grown in 1 day[Yan et al. Phys. Stat. Sol.

201, R27 (2004)]


OPPORTUNITIES AND CHALLENGES:

0

50

100

150

200

6 7 8 9 10 11

Volume (cm3/mol)

Pre

ssur

e (G

Pa)

Re

Ta

SingleSingle--crystal CVD anvils can crystal CVD anvils can generate generate multimegabarmultimegabar pressurespressures

X-RAY EOS

• Two runs: NSLS (EDX) APS (ADX)

• Beveled, A=100 µm B= 300 µm;θ =10º (CVD)

[W. Mao et al., Appl. Phys. Lett. 83, 5190 (2003)]

CVD single crystals are CVD single crystals are utratoughutratough and/or and/or ultrahardultrahard

OPPORTUNITIES AND CHALLENGES:Towards TPa Pressures with Large Volume Anvil Cells

[Yan et al. Phys. Stat. Sol. 201, R27(2004)]


OPPORTUNITIES AND CHALLENGES:OPPORTUNITIES AND CHALLENGES:Towards TPa Pressures with Large Volume Anvil Cells

2800 3000 3200 3400 3600 3800 4000

CVD

CVD anneal

Abs

orba

nce

Wavenumber (cm-1)

C-H stretching

• Unusual hydrogen impurity structure • Largely homogeneous based on IR mapping• Enhanced far-IR transparency on annealling• X-ray topography (X19) in progress

100 200 300 400 500 600 7000

5

10

IIa

Ib

Ib anneal

CVD

CVD anneal

Abs

orpt

ion

coef

ficie

nt (c

m-1)

Wavenumber (cm-1)

3 mm

Characterization of CVD diamond single crystals by synchrotron ICharacterization of CVD diamond single crystals by synchrotron IRR

IR Map 3000 cm-1


CONCLUSIONSCONCLUSIONS11. High pressure: a superb application of synchrotron IR . High pressure: a superb application of synchrotron IR

techniques, complementing hard xtechniques, complementing hard x--rays and other rays and other methods.methods.

2.2. An essential tool for uncovering new physics and An essential tool for uncovering new physics and chemistry of materials under extreme conditions.chemistry of materials under extreme conditions.

3. Numerous problems in Earth and planetary science can 3. Numerous problems in Earth and planetary science can now be addressed.now be addressed.

4. Particularly important are the new far4. Particularly important are the new far--IR developments IR developments and integrated multiand integrated multi--probe approaches.probe approaches.

5.5. Numerous new highNumerous new high--pressure technique developments pressure technique developments are coming on line to complement the new generation are coming on line to complement the new generation of synchrotron facilities: NSLSof synchrotron facilities: NSLS--IIII

6. The pressure parameter should be an integral part of 6. The pressure parameter should be an integral part of sample environments at beamlines throughout NSLSsample environments at beamlines throughout NSLS--II. II.

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