The New York Times, July 29, 2008

1. The New York Times, July 29, 2008

2. Classical and Quantum Theory of Glasses 1. Ancient (1980’s) T.R. Kirkpatrick, D. Thirumalai, R. Hall, Y. Singh, J.P. Stoessel 2. Modern (2000’s) X.Y. Xia, V. Lubchenko, J. Stevenson, J. Schmalian, R. Hall, R. Small Peter G. Wolynes

3. “…you had the impression they were trying to sell you an old car” --- Jean-Philippe Bouchard, as quoted in The New York Times, July 29, 2008

5. The Architecture of Aperiodic Crystals Model handbuilt by J.D. Bernal

12. 2 Δ F‡ = 4Tsc N1/3 Crystallization vs. Glassy Dynamics crystallite critical nucleus size F large surface cost N F(N) = - TscN + N1/2 Notice no energy gap. F(N) = -Δƒ N +  N2/3 (ΔEs - TSc), Free energy gap Glassy Barrier depends on Tsc alone! Crystal nucleation barrier depends on TF - T

15. Super Arrhenius temperature dependence of rates SiO2 Glassy Dynamics from a Mosaic of Energy Landscapes Temperature of Vanishing Entropy Lubchenko and Wolynes, Annu. Rev. Phys. Chem. 2007, 85:235-66.

16. RFOT theory predicts fragility parameter, m m from RFOT m from experiment

17. RFOT predicts the non-exponentiality parameter from fragility and thermodynamics Mosaic picture ξ ξ=4.5a

19. RFOT predictions of CRR size agree with experiment Berthier et al. inequality Berthier et al. Science (2005) 310, 1797 Data from: Bohmer et al. J. Chem. Phys. (1993) 99, 4201

20. Levinthal Meets Kauzmann! • Bare RFOT: • In RFOT theory σCRRis a universal function of log(τα/τ0) • Relaxation time = random search time of a correlated region • Adam-Gibbs assumes • σCRR = constant • (and small, typically)

21. Relaxation Time and the Complexity of Rearranging Regions Mode coupling theory with RFOT instanton vertex Bhattacharyya-Bagchi-Wolynes Berthier et al Science (2005) Capaccioli-Ruocco-Zamponi J. Phys. Chem. B (2008)

22. Shapes of CRR’s • Surface interaction energy favors compact shape • Shape entropy favors fractal shape Small surface area Large surface area Gebremichael et al. J. Chem. Phys 120, 4415

23. Shape transition signals crossover temperature Mode Coupling Transition Log( Viscosity , P) String Transition Sc(Tg)/Sc Same as Hagedorn transition in string theory!

24. Intermolecular forces and the glass transition R.W. Hall and PGW Self consistent phonon theory and liquid equation of state Plots mV and mP on the one hour time scale using the MGC equation of state

25. nb nb nb

26. Explicit magnetic analogies for structural glass -Jacob Stevenson -Rachel Small -Aleksandra Walczak -PGW Nucleation dynamics Self-Consistent Phonon Theory / Density functional Theory F(α) TSc α* α Large α frozen state Small α liquid state F(m) Dynamics equivalent to random Ising system escaping from the metastable state <h> m

27. Making the mapping explicit Glassy free energy from self consistent phonon theory P(hi) P(Jij) Compare to liquid state free energy Recover the direct mapping: Coloring gives flipping cost. Blue is the most stable

28. Constructing explicit magnetic analogies for glass forming liquids F(m) F(q) TSc <h> q* q m Is there replica symmetry breaking? Zero field phase diagram Migliorini-Berker, 1998

29. Relaxation time and free energy profile for reconfiguration coordinate N* = 130 Sc = 1.1kB Escaped state Transition state Initial state With facilitation effects: Xia-Wolynes, 2001

30. Increased mobility on free surfaces Particles on free surfaces feel reduced cage effect No mismatch penalty Free surface Mismatch penalty F‡surf = F‡bulk / 2 Stevenson-Wolynes (2008)

31. Surface mobility leads to high stability vapor deposited glasses On the same time scale, the surface layer can reach configurational entropy values half that of the bulk. F†surf = F†bulk / 2 IMC Vapor Deposited glasses can reach a maximum of twice the stability of bulk glasses sc Stevenson-Wolynes (2008) Ediger et al J. Phys. Chem. B (2008)

32. Vassily Lubchenko & PGW, JCP (2004) 121, 2852

34. Non-equilibrium aging effect is predicted from fragility within RFOT theory

35. After long-aging the mosaic is more heterogeneous “Ultra-slow” relaxations

36. Confrontation of Classical RFOT Theory with Observation

37. Some Relationships of RFOT Theory with Other Approaches RFOT Theory (Microscopic) Mode Coupling Theory Leutheusser, Götze Strings, Bhattacharya, Bagchi, PGW Phenomenological Mode Coupling Theory Yes, but a higher order effect Facilitation Andersen, etc. Frustrated Phase Transitions- icosahedratics, etc Nelson, Kivelson, etc.

38. Local libraries lead to tunneling resonances Lubchenko & PGW N* ΔE=0

39. Density of Resonances ε<<Tg

42. Direct spectroscopic evidence of complex structure of 2LS

45. Confrontation of Quantized RFOT Theory with Observation

47. Percolation clusters and strings • The surface of percolation clusters and strings scales with volume: b=αN. Percolation: Strings:

49. RFOT theory predicts dynamic fragility from thermodynamics Dm=590/(m-16) Bohmer, Ngai, & Angell, JCP, (1993)

50. Energy Landscapes Library Construction Nature of cooperatively rearranging regions Two Level Systems as Resonances Boson Peak Electrodynamics Beyond Semi-Classical Theory – Quantum Melting X.Y. Xia, UIUC/McKenzie Vas Lubchenko, UH Jake Stevenson, UCSD Joerg Schmalian, Iowa R. Silbey, MIT Classical and Quantum Glasses