Probing Water and other Liquids with LCLS-II - SLAC Portal ...

Water denser than iceProbing Water and other Liquids with LCLS-IIAnders Nilsson, SUNCAT Ctr for Interface Science and CatalysisDensity of the liquid higherthan the solidNormal liquid (ethanol, gasoline,etc)Solid more dense than liquid

The Blue Planet

Access to Clean WaterThe Challenge Climate for the Change World with Water Climate Issues ChangeGore, Inconvenient Truth

Water denser than iceDensity of the liquid higherthan the solidNormal liquid (ethanol, gasoline,etc)Solid more dense than liquid

Density MaximumNormal liquiddensityddddddddddddWaterSsssssssssssssssssssssss-50-25025 50 75 100Temperature/ °CAt the bottom of the glass is 4 °C water

High Heat CapacityIt stabilizes the temperature in the OceansOcean current stabilizes the climate

Anomalous Properties of WaterIsothermalCompressibilityHeat CapacityThermalexpansion=Vk B Tκ T =Nk B c p =Vk B TαDensity fluctuations Entropy fluctuations Cross of density andentropy fluctuationsDivergence towards a mysterious temperature of -45 °CP. Kumar, S. Han, H.E. Stanley, J. Phys.: Condens. Matter 21 (2009) 504108.

X-ray Spectroscopies and Scattering Data• XAS indicates predominant asymmetrical coordination withfewer H-bonds than in tetrahedral modelWernet et al., Science 304 (2004) 995• XES shows two motifs: strongly tetrahedraland very disorderedTokushima et al., Chem. Phys. Lett. 460 (2008) 387• SAXS shows fluctuating density inhomogeneityEnhanced upon coolingHuang et al., PNAS 106, 15214 (2009); 107, E45 (2010);JCP 133, 134504 (2010)•WAXS shows broad structural distributionsand shell-structure (~12 Å) consistent withtwo structural motifs (and with SAXS)Huang et al. Phys. Chem. Chem. Phys. 13, 19997 (2011)

IceOpen spaces where nomolecules are presentIf molecules move to fill theopen space there will be anincrease in the density

Summary room temperature to -20 °CStrongly Distorted is related to local High Density Liquid (HDL)Tetrahedral is related to local Low Density Liquid (LDL)HDL and LDL fluctuationsTwo local structural different motifs≈1nm length scales at room temperatureIncreasing length scale with decreasing temperatureA. Nilsson and L. G. M. Pettersson, Chem. Phys. 389, 1 (2011).

Snapshot from MD at -20 °CPerspective on waterChem. Phys. 389, 1 (2011).Blue: High tetrahedralityYellow: High densityBox side length 100 Å

Probing bulk water and ice crystallization in "no-mansland"; first results from the X-ray laser at StanfordCongcong Huang, Trevor McQueen, Jonas Sellberg, Hartawan Laksmono, Duane Loh, RaySierra, Christina Hampton, Dimitri Starodub, Dennis Nordlund, Martin Beye, Daniel Deponte 1 ,Andy Martin 1 , Andrew Barty 1 , Jan Feldkamp, Sebastian Boutet, Garth Williams, K. T. Wikfeldt 2 ,L. G. M. Pettersson 2, Mike Bogan and Anders NilssonSingle shot x-ray scattering50 femtosecond pulseSLAC National Accelerator Center/Stanford University Feb 20111Center for Free Electron Laser, Hamburg2Stockholm University

“No-Mans Land” below limit of homogeneous ice formationHomogenousIce NucleationLimit -38 °C-45 °C in “nomans land”ρ(HDA)=1.17 g/cm 3ρ(LDA)=0.94Low DensityAmorphous Ice (LDA)High DensityAmorphous Ice(HDA)ρ(Ih)=0.92ρ(Ic)=0.92H. E. STANLEY “Mysteries of Water” Les Houches Lecture, May 1998Originally Proposed P. H. Pool and H. E. Stanley et.al Nature 360, 324 (1992)

Stability LimitRetracing SpinodalLiquid no longer stableIce is instantaneous formed -45 °CDifferent Models2 nd critical point modelHDL-LDL Liquid TransitionWidom line maximum HDL-LDL fluctuations -45 °CR. J Speedy J. Phys. Chem. 86, 982 (1982)A. C. Angell, Nature 331, 206 (1988)P. H. Pool et al., Nature 360, 324 (1992)Variation vid Critical Point at O KS. Sastry et al., Phys. Rev. E 53 , 6144 (1996). )

X-ray Emission SpectroscopyHDLLDLLDLHDLProbing population of HDL and LDL using XESExperiment in October at SXR, collaboration with Wernet et al HZB

Probing water at higher pressures and glassy formsHomogenousIce NucleationLimit -38 °C-45 °C in “nomans land”ρ(HDA)=1.17 g/cm 3ρ(LDA)=0.94Low DensityAmorphous Ice (LDA)High DensityAmorphous Ice(HDA)ρ(Ih)=0.92ρ(Ic)=0.92H. E. STANLEY “Mysteries of Water” Les Houches Lecture, May 1998Originally Proposed P. H. Pool and H. E. Stanley et.al Nature 360, 324 (1992)

Much largerenhancements(fluctuations!)at lower TSAXS – Ambient to Supercooled RegimeAt low Q rangeS(Q) shows anunusual enhancementS 1Aζ + Q( Q) ∝ − 2 2F.T.Q1)k TnχBVery good fit to previous dataTHuang et al., PNAS 106, 15214 (2009); PNAS 107, E45 (2010); JCP 133, 134504 (2010)

Apparent Power Law – Widom LineCritical phenomena characterized by power laws with critical exponents.322nd critical point scenarioFluctuations between HDL/LDLPoole et al., Nature 360, 324 (1992).52Fit ζ to (apparent) powerlawξξ ε−νTIP4P-2005 simulationsBlue LDL Red HDLbased on inherent structure= 0withε T / T −1=sHuang et al. JCP 133, 134504 (2010)K. T. Wikfeldt et al. Phys. Chem. Chem. Phys, 13, 19918 (2011).

Probing correlation length in no-mans landWidom LineT2 nd critical pointPξWe need much higher intensity !!!T

Super hard x-ray diffraction study on water pair correlation functionAPS 11-ID-C: 115 keV photons and an amorphous Silicon area detectorCurrent CXIFourier TransformLong-range orderings(up to 1.4 nm) are visible!293 KCourtesy C. Benmore

Ordered StructuresEquilibrium PhenomenaDisordered StructuresNonequilibrium PhenomenaTransient StatesEra of Crystalline MatterConventional X-ray ProbesEra of Disordered MatterCoherent X-ray Probes1900 2000 futureCourtesy of H. Dosch

Coherent Diffraction Patternobtained from frozen liquid (glass)P. Wochner et al., PNAS 106, 11511 (2009)„Laser Speckles“

Hidden Local Symmetries fromHigher-Order Correlation Functions4-point correlationsMPI-MF DESY ESRFP. Wochner et al.PNAS 106, 11511 (2009)C Q(∆) = < I(Q,ϕ)I(Q,ϕ + ∆) > ϕ − < I(Q,ϕ) >2 ϕ< I(Q,ϕ) > 2 ϕ

Angular Correlations of H 2 ODetector Position 1 Detector Position 2 Detector Position 3∆ (º)∆ (º) ∆ (º)q (Å -1 )97.5 mm 122.5 mm 147.5 mmJan Feldkamp, Jonas Sellberg and Derek Mendez

Ultrafast XPCS using ‘Split Pulse’ ModeFemtoseconds to nanoseconds time resolutionUses high peak brilliancesplittersampletransversely coherentX-ray pulse from FELvariable delayContrastAnalyze contrastas f(delay time)sum of speckle patternsfrom prompt and delayed pulsesrecorded on CCD

Bonds vs. Entropylocalized bondsdelocalizedbondsBond EnergyEntropy

Perform pump-probeIR-THz and x-rayProbe stability and dynamics ofHDL and LDL structuresSelective excitations in libration bandProbe XES, SAXS, CXIPump-probeWaterIR spectraIceFrustrated Motion in H-bondsFrom Y. Maréchal, The Hydrogen Bond and theWater Molecule, Elsevier (2007)

Water and BiologyHydration layer in DNA and Proteins

Interfacial Water

Wish list LCLS II• High Intensity (>10 mJ) small focus for CXI experiments• Higher Energy 30-100 keV for large Q space (3 rd harmonics)• Detector with a uniform response• X-ray correlation spectroscopy from 100fs to ms• THz – IR pump• Soft x-ray dedicated liquid endstation• Stimulated emission• Different sample geometries, high pressure with a pulse source• End station for surfaces and interfaces, both soft and hard x-rays