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  1. Article ; Online: Microscopic understanding of the Johari-Goldstein β relaxation gained from nuclear γ-resonance time-domain-interferometry experiments.

    Ngai, K L

    Physical review. E

    2021  Volume 104, Issue 1-2, Page(s) 15103

    Abstract: Traditionally the study of dynamics of glass-forming materials has been focused on the structural α relaxation. However, in recent years experimental evidence has revealed that a secondary β relaxation belonging to a special class, called the Johari- ... ...

    Abstract Traditionally the study of dynamics of glass-forming materials has been focused on the structural α relaxation. However, in recent years experimental evidence has revealed that a secondary β relaxation belonging to a special class, called the Johari-Goldstein (JG) β relaxation, has properties strongly linked to the primary α relaxation. By invoking the principle of causality, the relation implies the JG β relaxation is fundamental and indispensable for generating the α relaxation, and the properties of the latter are inherited from the former. The JG β relaxation is observed together with the α relaxation mostly by dielectric spectroscopy. The macroscopic nature of the data allows the use of arbitrary or unproven procedures to analyze the data. Thus the results characterizing the JG β relaxation and the relation of its relaxation time τ_{β} to the α-relaxation time τ_{α} obtained can be equivocal and controversial. Coming to the rescue is the nuclear resonance time-domain-interferometry (TDI) technique covering a wide time range (10^{-9}-10^{-5}s) and a scattering vector q range (9.6-40nm^{-1}). TDI experiments have been carried out on four glass formers, ortho-terphenyl [M. Saito et al., Phys. Rev. Lett. 109, 115705 (2012)10.1103/PhysRevLett.109.115705], polybutadiene [T. Kanaya et al., J. Chem. Phys. 140, 144906 (2014)10.1063/1.4869541], 5-methyl-2-hexanol [F. Caporaletti et al., Sci. Rep. 9, 14319 (2019)10.1038/s41598-019-50824-7], and 1-propanol [F. Caporaletti et al., Nat. Commun. 12, 1867 (2021)10.1038/s41467-021-22154-8]. In this paper the TDI data are reexamined in conjunction with dielectric and neutron scattering data. The results show the JG β relaxation observed by dielectric spectroscopy is heterogeneous and comprises processes with different length scales. A process with a longer length scale has a longer relaxation time. TDI data also prove the primitive relaxation time τ_{0} of the coupling model falls within the distribution of the TDI q-dependent JG β-relaxation times. This important finding explains why the experimental dielectric JG β-relaxation times τ_{β}(T,P) is approximately equal to τ_{0}(T,P) as found in many glass formers at various temperature T and pressure P. The result, τ_{β}(T,P)≈τ_{0}(T,P), in turn explains why the ratio τ_{α}(T,P)/τ_{β}(T,P) is invariant to changes of T and pressure P at constant τ_{α}(T,P), the α-relaxation time.
    Language English
    Publishing date 2021-08-13
    Publishing country United States
    Document type Journal Article
    ZDB-ID 2844562-4
    ISSN 2470-0053 ; 2470-0045
    ISSN (online) 2470-0053
    ISSN 2470-0045
    DOI 10.1103/PhysRevE.104.015103
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  2. Article ; Online: Why the Brillouin Light Scattering Relaxation Times of Molten Zinc Chloride Are Shorter and Weaker in Temperature Dependence than the Structural Relaxation Times from Depolarized Light and Neutron Spin Echo Spectroscopy.

    Ngai, K L

    The journal of physical chemistry. A

    2021  Volume 125, Issue 13, Page(s) 2759–2763

    Abstract: A longstanding problem in the Brillouin light scattering (BLS) study of polymers is the relaxation times ... ...

    Abstract A longstanding problem in the Brillouin light scattering (BLS) study of polymers is the relaxation times τ
    Language English
    Publishing date 2021-03-24
    Publishing country United States
    Document type Journal Article
    ISSN 1520-5215
    ISSN (online) 1520-5215
    DOI 10.1021/acs.jpca.1c00761
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  3. Article ; Online: The origin of the faster mechanism of partial enthalpy recovery deep in the glassy state of polymers.

    Ngai, K L

    Physical chemistry chemical physics : PCCP

    2021  Volume 23, Issue 24, Page(s) 13468–13472

    Abstract: A novel finding made by Cangialosi and coworkers in the physical aging of several polymers way below the glass transition temperature Tg is that equilibrium recovery occurs by reaching a plateau in the enthalpy with partial enthalpy recovery. This ... ...

    Abstract A novel finding made by Cangialosi and coworkers in the physical aging of several polymers way below the glass transition temperature Tg is that equilibrium recovery occurs by reaching a plateau in the enthalpy with partial enthalpy recovery. This observation points to the existence of a much faster mechanism capable of partial equilibrium recovery deep in the glassy state. A similar phenomenon was found in different glassy materials. The generality of the phenomenon indicates that the faster mechanism of equilibrium recovery is universal and fundamental. In this paper the faster mechanism is identified to be the universal JG β-relaxation having dynamic and thermodynamic properties analogous to the α-relaxation, and thus capable of effecting enthalpy and volume recovery far below Tg in several high-Tg polymers. The JG β-relaxation is also the mechanism responsible for the first step of two steps in the approach to equilibrium found in another polymer with much lower Tg. The Coupling Model is used to explain why the first step transpires far below Tg in some polymers but much closer to Tg in another polymer.
    Language English
    Publishing date 2021-06-09
    Publishing country England
    Document type Journal Article
    ZDB-ID 1476244-4
    ISSN 1463-9084 ; 1463-9076
    ISSN (online) 1463-9084
    ISSN 1463-9076
    DOI 10.1039/d1cp01445e
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  4. Article ; Online: Accounts of the changes in dynamics of hydrogen-bonded materials by pressure, nanoconfinement, and hyperquenching.

    Ngai, K L

    Physical review. E

    2020  Volume 102, Issue 3-1, Page(s) 32606

    Abstract: A hydrogen-bonding network or hydrogen-bonded cluster is formed in many hydrogen-bonded glass formers. It determines the dynamics of structural α relaxation and the Johari-Goldstein (JG) β relaxation because breaking of hydrogen bonds is the prerequisite. ...

    Abstract A hydrogen-bonding network or hydrogen-bonded cluster is formed in many hydrogen-bonded glass formers. It determines the dynamics of structural α relaxation and the Johari-Goldstein (JG) β relaxation because breaking of hydrogen bonds is the prerequisite. However, the networks and clusters can be substantially reduced or totally removed in the liquid state by high temperature accompanying the applied high pressure in experiments, and in the glassy state by hyperquenching the liquid under pressure. By confining the glass former in nanometer spaces, the extended network cannot form, and in addition the finite size effect limits the growth of the length scale of the α relaxation on lowering temperature. Any of these actions will modify the structure of the original hydrogen-bonded glass former, and also the intermolecular interaction governing the relaxation processes. Consequently the dynamics of the structural α relaxation and the JG β relaxation, as well as the relation between the two processes, are expected to change. An important advance in the study of the dynamics of glass-forming materials is the existence of the strong connection between the α relaxation and the JG β relaxation. In particular, the ratio of their relaxation times, t_{α}(T)/t_{β}(T), is quantitatively determined by the exponent of the Kohlrausch relaxation function of the α relaxation. This property is valid in hydrogen-bonded glass formers as well as in non-hydrogen-bonded glass formers. The interesting question is whether this property continues to hold after the hydrogen-bonded glass former has been modified by high temperature under high pressure, nanoconfinement, and hyperquenching under pressure. Remarkably, the answer is positive as concluded from the analyses of the data in several hydrogen-bonded glass formers reported in this paper. So far the main theoretical explanation of this property has been the coupling model.
    Language English
    Publishing date 2020-10-20
    Publishing country United States
    Document type Journal Article
    ZDB-ID 2844562-4
    ISSN 2470-0053 ; 2470-0045
    ISSN (online) 2470-0053
    ISSN 2470-0045
    DOI 10.1103/PhysRevE.102.032606
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  5. Article ; Online: Relations between the Structural α-Relaxation and the Johari-Goldstein β-Relaxation in Two Monohydroxyl Alcohols: 1-Propanol and 5-Methyl-2-hexanol.

    Ngai, K L / Wang, Li-Min

    The journal of physical chemistry. B

    2019  Volume 123, Issue 3, Page(s) 714–719

    Abstract: The hydrogen-bonded monohydroxyl alcohols form a large class of glass formers studied more than one hundred years, and still the structure and dynamics have continued to be a research problem. Recent advance suggests a hydrogen-bonded transient ... ...

    Abstract The hydrogen-bonded monohydroxyl alcohols form a large class of glass formers studied more than one hundred years, and still the structure and dynamics have continued to be a research problem. Recent advance suggests a hydrogen-bonded transient supramolecular structure, which is the origin of the Debye relaxation dominating the dielectric loss spectra of many monohydroxyl alcohols. Obscured by the slower Debye relaxation, the structural α-relaxation is either not resolved or showing up as a shoulder and the supposedly universal Johari-Goldstein (JG) β-relaxation is not always observed. Thus, properties of the α-relaxation and the JG β-relaxation as well as the strong connection between the two relaxations generally observed in other classes of glass formers are not commonly known in the monohydroxyl alcohols. Notwithstanding, extremely broadband dielectric relaxation and high-precision light scattering experiments published recently have resolved the α-relaxation and a secondary relaxation in two archetypal monohydroxyl alcohols, 1-propanol and 5-methyl-2-hexanol (5M2H) by Gabriel et al. We analyzed their experimental data and applied the Coupling Model to show that the secondary relaxations in 1-propanol and 5M2H are JG β-relaxations with strong connection to the α-relaxation. The result is novel because it is not known before whether the secondary relaxations of these two monohydroxyl alcohols are JG β-relaxation involving the entire molecule or are intramolecular relaxations. On the basis of this conclusion, we predict that the secondary relaxation is pressure-dependent and the ratio τ
    Language English
    Publishing date 2019-01-14
    Publishing country United States
    Document type Journal Article
    ISSN 1520-5207
    ISSN (online) 1520-5207
    DOI 10.1021/acs.jpcb.8b11453
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  6. Article ; Online: Interpreting the nonlinear dielectric response of glass-formers in terms of the coupling model.

    Ngai, K L

    The Journal of chemical physics

    2015  Volume 142, Issue 11, Page(s) 114502

    Abstract: Nonlinear dielectric measurements at high electric fields of glass-forming glycerol and propylene carbonate initially were carried out to elucidate the dynamic heterogeneous nature of the structural α-relaxation. Recently, the measurements were extended ... ...

    Abstract Nonlinear dielectric measurements at high electric fields of glass-forming glycerol and propylene carbonate initially were carried out to elucidate the dynamic heterogeneous nature of the structural α-relaxation. Recently, the measurements were extended to sufficiently high frequencies to investigate the nonlinear dielectric response of faster processes including the so-called excess wing (EW), appearing as a second power law at high frequencies in the loss spectra of many glass formers without a resolved secondary relaxation. While a strong increase of dielectric constant and loss is found in the nonlinear dielectric response of the α-relaxation, there is a lack of significant change in the EW. A surprise to the experimentalists finding it, this difference in the nonlinear dielectric properties between the EW and the α-relaxation is explained in the framework of the coupling model by identifying the EW investigated with the nearly constant loss (NCL) of caged molecules, originating from the anharmonicity of the intermolecular potential. The NCL is terminated at longer times (lower frequencies) by the onset of the primitive relaxation, which is followed sequentially by relaxation processes involving increasing number of molecules until the terminal Kohlrausch α-relaxation is reached. These intermediate faster relaxations, combined to form the so-called Johari-Goldstein (JG) β-relaxation, are spatially and dynamically heterogeneous, and hence exhibit nonlinear dielectric effects, as found in glycerol and propylene carbonate, where the JG β-relaxation is not resolved and in D-sorbitol where it is resolved. Like the linear susceptibility, χ1(f), the frequency dispersion of the third-order dielectric susceptibility, χ3(f), was found to depend primarily on the α-relaxation time, and independent of temperature T and pressure P. I show this property of the frequency dispersions of χ1(f) and χ3(f) is the characteristic of the many-body relaxation dynamics of interacting systems which are governed solely by the intermolecular potential, and thermodynamic condition plays no role in this respect. Although linked to χ3(f), dynamic heterogeneity is one of the parallel consequences of the many-body dynamics, and it should not be considered as the principal control parameter for the other dynamic properties of glassforming systems. Results same as χ3(f) at elevated pressures had been obtained before by molecular dynamics simulations from the four-points correlation function and the intermediate scattering function. Naturally all properties obtained from the computer experiment, including dynamics heterogeneity, frequency dispersion, the relation between the α- and JG β-relaxation, and the breakdown of the Stokes-Einstein relation, are parallel consequences of the many-body relaxation dynamics governed by the intermolecular potential.
    Language English
    Publishing date 2015-03-21
    Publishing country United States
    Document type Journal Article
    ZDB-ID 3113-6
    ISSN 1089-7690 ; 0021-9606
    ISSN (online) 1089-7690
    ISSN 0021-9606
    DOI 10.1063/1.4913980
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  7. Article ; Online: Comparative analysis of dielectric, shear mechanical and light scattering response functions in polar supercooled liquids.

    Ngai, K L / Wojnarowska, Z / Paluch, M

    Scientific reports

    2021  Volume 11, Issue 1, Page(s) 22142

    Abstract: The studies of molecular dynamics in the vicinity of liquid-glass transition are an essential part of condensed matter physics. Various experimental techniques are usually applied to understand different aspects of molecular motions, i.e., nuclear ... ...

    Abstract The studies of molecular dynamics in the vicinity of liquid-glass transition are an essential part of condensed matter physics. Various experimental techniques are usually applied to understand different aspects of molecular motions, i.e., nuclear magnetic resonance (NMR), photon correlation spectroscopy (PCS), mechanical shear relaxation (MR), and dielectric spectroscopy (DS). Universal behavior of molecular dynamics, reflected in the invariant distribution of relaxation times for different polar and weekly polar glass-formers, has been recently found when probed by NMR, PCS, and MR techniques. On the other hand, the narrow dielectric permittivity function ε*(f) of polar materials has been rationalized by postulating that it is a superposition of a Debye-like peak and a broader structural relaxation found in NMR, PCS, and MR. Herein, we show that dielectric permittivity representation ε*(f) reveals details of molecular motions being undetectable in the other experimental methods. Herein we propose a way to resolve this problem. First, we point out an unresolved Johari-Goldstein (JG) β-relaxation is present nearby the α-relaxation in these polar glass-formers. The dielectric relaxation strength of the JG β-relaxation is sufficiently weak compared to the α-relaxation so that the narrow dielectric frequency dispersion faithfully represents the dynamic heterogeneity and cooperativity of the α-relaxation. However, when the other techniques are used to probe the same polar glass-former, there is reduction of relaxation strength of α-relaxation relative to that of the JG β relaxation as well as their separation. Consequently the α relaxation appears broader in frequency dispersion when observed by PCS, NMR and MR instead of DS. The explanation is supported by showing that the quasi-universal broadened α relaxation in PCS, NMR and MR is captured by the electric modulus M*(f) = 1/ε*(f) representation of the dielectric measurements of polar and weakly polar glass-formers, and also M*(f) compares favorably with the mechanical shear modulus data G*(f).
    Language English
    Publishing date 2021-11-12
    Publishing country England
    Document type Journal Article
    ZDB-ID 2615211-3
    ISSN 2045-2322 ; 2045-2322
    ISSN (online) 2045-2322
    ISSN 2045-2322
    DOI 10.1038/s41598-021-01191-9
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  8. Article ; Online: Isochronal superpositioning of the caged dynamics, the α, and the Johari-Goldstein β relaxations in metallic glasses.

    Ren, N N / Guan, P F / Ngai, K L

    The Journal of chemical physics

    2021  Volume 155, Issue 24, Page(s) 244502

    Abstract: The superposition of the frequency dispersions of the structural α relaxation determined at different combinations of temperature T and pressure P while maintaining its relaxation time ... ...

    Abstract The superposition of the frequency dispersions of the structural α relaxation determined at different combinations of temperature T and pressure P while maintaining its relaxation time τ
    Language English
    Publishing date 2021-12-31
    Publishing country United States
    Document type Journal Article
    ZDB-ID 3113-6
    ISSN 1089-7690 ; 0021-9606
    ISSN (online) 1089-7690
    ISSN 0021-9606
    DOI 10.1063/5.0072527
    Database MEDical Literature Analysis and Retrieval System OnLINE

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  9. Article: Why the Relaxation Times of Polymers from Brillouin Light Spectroscopy Are Much Shorter than the Primary α-Relaxation Times

    Ngai, K. L / Fytas, George

    Macromolecules. 2019 Oct. 28, v. 52, no. 21

    2019  

    Abstract: Brillouin light spectroscopy (BLS) of polymers recorded much shorter relaxation times over the same temperature range than those obtained from other spectroscopies, including dielectric relaxation, dynamic light scattering, depolarized Rayleigh ... ...

    Abstract Brillouin light spectroscopy (BLS) of polymers recorded much shorter relaxation times over the same temperature range than those obtained from other spectroscopies, including dielectric relaxation, dynamic light scattering, depolarized Rayleigh scattering, NMR, and molecular dynamics simulations. This is an anomaly because a priori BLS is thought to monitor the structural α-relaxation of polymers like all the other techniques. First noted in 1977, the anomaly was repeatedly confirmed, but it has not been explained, and it remains a puzzling finding in amorphous polymers. In this paper, we explain this longstanding anomaly by the Coupling Model (CM), in conjunction with the fact that the α-relaxation of polymers is nonexponential at the relatively high temperatures of BLS measurements. The CM has the primitive relaxation, which is part of the Johari–Goldstein (JG) β-relaxation, and the precursor of the structural α-relaxation. The calculated primitive relaxation times match the BLS relaxation times quantitatively. This indicates that the primitive relaxation together with the JG β-relaxation of polymers is responsible for the phonon dispersion at hypersonic (GHz) frequencies, whereas the other spectroscopies probe mainly the α-relaxation. Additional support comes from the quasielastic neutron scattering experiment in the same polymer in which the primitive relaxation/JG β relaxation was directly observed with relaxation times in agreement with the calculated ones as well as the BLS relaxation times. Thus, the longstanding anomaly of polymers observed by BLS now has an explanation.
    Keywords light scattering ; molecular dynamics ; neutron diffraction ; nuclear magnetic resonance spectroscopy ; polymers ; simulation models ; temperature
    Language English
    Dates of publication 2019-1028
    Size p. 8305-8311.
    Publishing place American Chemical Society
    Document type Article
    ZDB-ID 1491942-4
    ISSN 1520-5835 ; 0024-9297
    ISSN (online) 1520-5835
    ISSN 0024-9297
    DOI 10.1021/acs.macromol.9b01849
    Database NAL-Catalogue (AGRICOLA)

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  10. Article ; Online: The structural α-relaxation times of prilocaine confined in 1 nm pores of molecular sieves: quantitative explanation by the coupling model.

    Ngai, K L / Wojnarowska, Z / Paluch, Marian

    Physical chemistry chemical physics : PCCP

    2020  Volume 22, Issue 17, Page(s) 9257–9261

    Abstract: The molecular glass-former and pharmaceutical, prilocaine, distinguishes itself by exhibiting seven general and fundamental dynamic and thermodynamic properties [Z. Wojnarowska, et al., J. Phys. Chem. B, 2015, 39, 12699.], all of which have been ... ...

    Abstract The molecular glass-former and pharmaceutical, prilocaine, distinguishes itself by exhibiting seven general and fundamental dynamic and thermodynamic properties [Z. Wojnarowska, et al., J. Phys. Chem. B, 2015, 39, 12699.], all of which have been explained using the coupling model. What has not been studied before are the changes in properties of the structural α-relaxation of prilocaine when subjected to extreme nano-confinement in spaces with a size of about 1 nm. Recently, Ruis et al. [G. N. Ruiz, et al., Phys. Chem. Chem. Phys., 2019, 21, 15576.] measured the α-relaxation times, τ
    Language English
    Publishing date 2020-04-20
    Publishing country England
    Document type Journal Article
    ZDB-ID 1476244-4
    ISSN 1463-9084 ; 1463-9076
    ISSN (online) 1463-9084
    ISSN 1463-9076
    DOI 10.1039/d0cp00282h
    Database MEDical Literature Analysis and Retrieval System OnLINE

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