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Simple theory of viscosity in liquids

Article  in  PHYSICAL REVIEW E · December 2018

DOI: 10.1103/PhysRevE.98.063005

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 A Simple Theory of Viscosity in Liquids

Jean Bellissard*
School of Mathematics and School of Physics, Georgia Institute of Technology, Atlanta GA,
USA, and
Fachbereich Mathematik und Informatik, Westfälische Wilhelms-Universität, Münster, Germany

Takeshi Egami
Department of Materials Science and Engineering and Department of Physics and Astronomy,
University of Tennessee, Knoxville, TN 37996, USA, and
Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA

*
E-mail address: jeanbel@math.gatech.edu

Abstract
A simplistic model of atomic dynamics in liquid, based on the concept of dynamic fluctuations in
local atomic connectivity, is proposed to elucidate the temperature variation of the viscosity of a
material in its liquid phase. Within the simplifications and hypothesis made to define the model,
it is possible to explain the crossover from a simple liquid to a cooperative liquid and covariance
of viscosity near the glass transition temperature. The model is a mechanical analog of the
Drude model for the electric transport in metal.

1
1. Introduction
Viscosity, η, of a liquid near the melting point is of the order of 10-3 Pa.s, whereas the
glass transition is defined by η reaching 1012 Pa.s [1]. The origin of this rapid change in
viscosity over a relatively small range of temperature is crucially related to the unsolved problem
regarding the nature of the glass transition [2, 3]. In spite of numerous attempts to explain its
origin [4-9] there is no broad agreement on this subject. Whereas much attention is currently
focused on the behavior of highly viscous supercooled liquids, in our view the most important
feature of the viscosity is the crossover from the Arrhenius to super-Arrhenius behavior which
occurs at a temperature, T*, much higher than the glass transition temperature, Tg. Kivelson
noted that the temperature dependence of the activation energy is universal if T* is used to scale
temperature [6]. The functional form of the universal behavior explains quite well the measured
viscosity of a large number of metallic alloy liquids [10]. Once the temperature dependence of
the viscosity becomes super-Arrhenius and the activation energy keeps increasing with
decreasing temperature, and it is a natural course of action that viscosity diverges at a finite
temperature. The glass transition is merely a consequence of this crossover. Therefore in this
line of argument the crucial element for understanding the glass transition is not the glass
transition itself but the nature and origin of this crossover phenomenon.
Kivelson proposed that T* is the freezing temperature of a phase to which the liquid
never reaches because of frustration [6]. Because of its intrinsic frustration long-range order of
such a phase cannot be achieved, but short-range dynamic fluctuations into this phase become
more prevalent as temperature is lowered, resulting in increased viscosity and ultimate jamming
into a glassy state. An example of the frustrated phase is the icosahedral state [4, 11]. Whereas a
quasi-crystal is a solid with icosahedral symmetry, it is a stoichiometric crystalline compound in
six dimensions which is formed only for a number of specific compositions [12]. For a liquid
with a composition other than these specific compositions the icosahedral order is geometrically
frustrated [4], and cannot form long-range order. But the particular local order of the frustrated
phase depends on composition. For instance for a poly-dispersed hard-sphere colloids the
fluctuating phase is a mixture of the icosahedral phase and the f.c.c. phase [13]. However, the
hypothesis that T* is the freezing temperature of the frustrated phase has not been confirmed.
On the other hand a different interpretation of the crossover phenomenon was proposed
based upon the phonon dynamics [14]. In this view the crossover occurs when the mean-free

2
path of shear phonon, ξ = cTτM, where cT is the velocity of a transverse phonon and τM is the
Maxwell relaxation time, becomes shorter than the mean atomic distance, the bulk of shear
phonons are localized. In other words above the crossover temperature, TA = T*, the structure is
fluctuating so fast that phonons cannot propagate and become overdamped. Only below TA
atoms can interact via phonons and atomic dynamics becomes cooperative. In this paper we
propose a simple model to quantify this dynamic crossover phenomenon based on the dynamics
of atomic connectivity network. We define the structure of liquid in terms of the atomic
connectivity network [15], and describe its dynamics by the action of cutting and forming the
atomic bond [16]. The crossover occurs as a consequence of competition between phonons and
bond cutting. This model is a mechanical analog of the Drude model for the electric transport in
metal. The work presented here is a small brick added to the knowledge, hoping that it will open
the door to a more accurate theory liable to explain the mystery of glass transition. However,
several evidences point toward this model providing some universal results: (a) it explains the
crossover phenomenon, (b) it introduces a parameter that permits to distinguish between strong
and fragile glasses, and (c) it explains the precipitous increase in viscosity below the crossover
temperature. In addition, while being first motivated by the study of bulk metallic glasses, it
could be relevant in other areas, such as colloids [17], usual glassy materials in their liquid
phase, or even quantum fluids [18].

2. The model
2.1. Structure and dynamics of liquid
Liquid and glass has no symmetry in the atomic structure. Thus it is difficult to describe
the structure and relate it to properties, even when we know the positions of all atoms at time t,
Ri(t). Experimentally the only the pair density correlation function (PDF), g(r), can be readily
obtained through the Fourier-transformation of the structure function, S(Q), which can be
determined by diffraction [19]. However, the PDF is a one-dimensional function, and does not
have sufficient informational content to determine a three-dimensional structure. To describe the
three-dimensional structure usually a model is constructed using a phenomenological interatomic
potential, and the results are analyzed in terms of the Voronoi polyhedra [15, 20], which is an
example of the Delone set [21, 22], as discussed in Appendix 1. The atomic connectivity is

3
defined by atoms which share a Voronoi face. The state of atomic connectivity is expressed in
terms of the Delone graph.
Now the Delone graph describes the state of atomic connectivity at a time. We now
consider how it evolves with time to describe its dynamics. The action of changing the
connectivity of the Delone graph is called Pachner moves discussed in Appendix 2 [21 – 24].
Such a move requires local atomic rearrangement which squeezes atoms and increases the
potential energy. It represents a move from one local equilibrium to another, crossing over an
energy barrier. In terms of the energy landscape it corresponds to crossing a saddle point [7]. In
high temperature liquid this process was shown to be the elementary process of excitation [14,
16], and was named “anankeon” [16]. They happen at unpredictable times, so that their dynamic
is more efficiently described in terms of a Markov process. Hence the corresponding stress felt
by each atom is constantly varying under the stress of circumstances, a concept that can be
translated by the word “anagkeia” in Greek. Associated with this concept was the Greek goddess
Ananke, expressing the fate or destiny, due to uncontrollable forces, constraints, necessity.
Hence the name “anankeon” associated with these stress induced unpredictable atomic moves.

2.2. A Toy Model.

What happens in the liquid state? Phonons still exist in liquids as in solids. However
phonons with short wave lengths, comparable to the inter-atomic distance, are strongly damped
in the liquid phase at high temperature. Whenever the typical time scale characterizing the
anankeon dynamics is comparable to the phonon period, the phonon has no time to oscillate and
it is overdamped. The present model investigates this damping more quantitatively. To proceed,
the same intuition will be followed as in the original paper of Drude on electronic transport in
metals [25]. In order to make the model computable, it will be assumed that it describes the
mechanical fate of a given atom: (i) as long as the topology of atomic connectivity remain
unchanged, this atom is located near the minimum of a local potential well, and it will oscillate,
harmonically, with a frequency given by the local curvature of the well, (ii) then at random times
(Poissonian distribution) the atom jumps, finding itself, after the jump in a new potential well,
with a new local curvature and a new initial location relative to the new equilibrium position and
a new initial velocity (phase-space position). Hence, the curvature of potential well (expressed
in terms of the frequency of oscillation) will be considered as a random variable with a fixed

4
average and a given covariance σ, which will be shown to be the most important parameter.
Similarly, the new relative initial phase-space position, after the jump, will also be chosen
randomly according to a Maxwell-Boltzmann distribution. To make the model even more
computable, it will be assumed that only one degree of freedom of oscillation is allowed (local
Einstein model). It will be seen that, even though this model is so simplistic, it exhibits a
transition between two time-scales as σ decreases. The computation of correlation functions, like
viscosity, shows that this change of scale may affect the viscosity in an essential way.

2.3. Anankeons in Glass: the STZ-Theory.

The deformation behavior of metallic glass was successfully described by the shear
transformation zone (STZ) theory, proposed by Argon [26] and extended by Langer [27 – 30].
The idea is that during plastic deformation, the local groups of atoms form droplets, STZ, in
which the solid really behaves like a liquid. Using the density of STZ as a variable, Langer et al.
proposed a system of effective equation at the macroscopic scale that are modeling the behavior
of the material under stress with a good accuracy. At the atomic scale numerical simulation
show that these STZ's are the result of a cascade or avalanche of atomic swaps, namely of
anankeons, [31], starting at a random site, called the germ. This initial anankeon induces other in
its neighborhood, because of the disruption created by the propagation of the stress induced by
such swaps. The cascade looks like a local catastrophic event, occurring during a very short
time, leading to the building of the local liquid-like droplets. The time scale representing the
time necessary to create an STZ is however long in comparison with the typical time scale of the
anankeon. Thus the cascade is not a collective phenomenon, but simply a succession of separate
anankeon events induced by the stress field created by the preceding deformation events. A
model for such a cascade of event was proposed in [31, 32].

3. Liquids at High Temperature as a Perfect Anankeon Gas

In our approach the structure of glass or liquid is described by the Delone graph which
specifies the topology of atomic connectivity. The Delone graph, however, does not have an
energy scale, whereas in order to calculate thermodynamic properties we need the knowledge of
the energy scale. A convenient way to introduce the energy scale to the Delone graph is to use

5
the concept of the atomic-level stresses [33]. The atomic-level stress tensor for an atom i, σ i , is

defined by

1
σ iαβ = ∑ f αrβij ij
, (1)
Vi j

where α and β refer to Cartesian indices, Vi is the local atomic volume of atom i, and fij and rij
α β

are the α and β components of force and distance between atoms i and j [34, 35]. Its trace gives
the atomic-level pressure

1 xx
pi =
3
(σ i + σ iyy + σ izz ) , (2)

whereas five other combinations give the shear, or deviatory, stresses, τni, n = 1 …5. The origin
of the atomic-level stress is the atomic-level misfit between the size of the atom and the size and
shape of the atomic site [33]. For instance if the atom is larger than the site it is placed it is
under compressive pressure. Thus they are directly connected to the topology of the neighboring
atoms which defines the size and shape of the atomic site. For instance the pressure is linearly
related to the number of nearest neighbors, the coordination number [36].
The stress tensor has six components for each atom, however, because of the identity fij =
- fji, the total number of free components is 3N, equal to the positional degree of freedom. For
this reason the equi-partition theorem holds for the stress in liquid [37, 38];
p2 τ n2 kT
= = , (3)
2B 2G 4
where B and G are the bulk and shear moduli. The distribution of local stress is Gaussian [39].
In the liquid state the atomic-level stresses fluctuate with time because the neighbors are
dynamic. In high-temperature liquid phonons are overdamped, and the mechanism of structural
change is anankeon excitation. Therefore a high-temperature liquid can be modeled a free gas of
anankeons. The degree of freedom associated with each anankeon will be given in terms of an
atomic stress tensor. Their Gaussian distribution observed in the numerical results can be
interpreted in terms of a Gibbs state describing the thermal equilibrium in a statistical mechanical
approach. If the atomic stress are uncorrelated, it becomes possible to compute the partition
function Z(T;N) of a volume of liquid containing N atoms. Note, however, an anankeon

6
excitation affects the stress tensors at two atoms involved in each atomic bond. Thus the part of
the partition function regarding the potential energy is Z(T;N) = Z1(T)N/2, where
⎛ ⎞
− β ⎜ p 2 2 B + ∑τ n2 2 G ⎟
⎜ ⎟ 1
Z1 (T ) = ∫ e ⎝ n ⎠
dσ , β = . (4)
k BT

The domain of integration is the space of all real symmetric d × d matrices, representing a
possible stress tensor. This Gaussian integral is easy to compute giving Z1(T) = Td(d+1)/4,
where is a constant depending on B and G, but independent of the temperature. The Clausius
entropy is given by S = kB ln(Z(N; T)) leading to the following expression of the contribution of
the potential energy to the heat capacity, Cv,p = cdNkB/2 where cd = d(d+1)/4, which is 3 in 3D.
Adding the contribution from the kinetic energy, Cv,k = cdNkB/2, we obtain the total specific
heat, Cv = cdNkB. Accordingly the system follows a Law of Dulong-Petit, just as the contribution
of phonons in crystal. However, the physical origin is different in liquid, because the main
degree of freedom associated with atoms are the atomic stress. Hence a liquid at high
temperatures can be seen as a perfect gas of anankeons. This prediction gave a satisfactory
answer to the experimental observation [40] of the saturation of the heat capacity at high
temperature.

4. Phonon-Anankeon Interaction
What happens at lower temperature, near the glass transition? The following model will
show that as the temperature decreases, the vibration modes are constraining the shape of local
clusters, so as to change the viscosity is a non-trivial way.

4.1. Time Scales

Because the dynamics plays such an important role in explaining the difference between
solids and liquids, the various relevant time scales ought to be discussed. The most elementary is
τLC, where LC stands for local configuration, representing the time required between two
consecutive Pachner moves. It corresponds to the anankeon relaxation time. The next time scale
is called Maxwell relaxation time τM = η/G [41] where η is the viscosity and G is the high
∞ ∞

frequency shear modulus. The Maxwell relaxation time represents the time scale below which
the system behaves like a solid and beyond which it can be considered as a liquid. Through

7
classical as well as ab initio molecular dynamics simulation on various metallic liquids it was
found that τM = τLC at high temperatures [14]. They obey the Arrhenius law,
τ M = τ LC = τ ∞ eW k T . B
(5)

However, below the crossover temperature, TA (= T*) the equality τM = τLC breaks down, and τM
becomes super-Arrhenius, whereas τLC remains Arrhenius [42]. Near the glass transition point,
there is a significant discrepancy between τM and τLC. This is the discrepancy that the present
model is going to describe. It seems natural, then, to choose τLC as the basic time scale for
modeling.

4.2. The toy model for anankeon-phonon interaction

We adopt the Einstein model for phonon, and assume ωE,i is the local Einstein frequency
of the atom i. Around an atom anankeon excitation occurs randomly with the average interval of
τLC. Thus the distribution of the time interval between anankeon excitation should have an
exponential distribution. Then the probability that anankeon is excited within the time τ is,
1 τ
P (τ ) = ∫ e −t τ LC dt . (6)
τ LC 0

Anankeon excitation involving the bond between atoms i and j changes the atomic-level stress
tensor of the atom i and j, σ i and σ j , and ωE,i and ωE,j by Δωi,n and Δωj,n. Here n denotes the

sequence of anankeon excitation (-∞ < n < ∞). It is reasonable to assume that Δωi,n is also a
random variable. Its average and variance are given by
12
1 ⎛ 1 2 ⎞
ω = ∑ ωE ,i , Δω = ⎜ ∑ ( Δωi ,n ) ⎟ . (7)
N i ⎝ N i ⎠

4.3. Viscosity
The viscosity is given by the fluctuation-dissipation theorem as [41]
V
η= Cσ ( t ) dt , (8)
k BT ∫
where V is the volume of the liquid, T temperature, and C is a shear stress correlation function,
σ

Cσ (t ) = σ xy ( 0)σ xy (t ) . (9)

8
In terms of the atomic-level stresses [34],
ρ0
Cσ ( t ) = ∑VV i j σ ixy ( 0 )σ xyj (t ) . (10)
V i, j

Using the approximation in Ref. 43,

νρ0 2
Cσ (t ) = ∑ (V ) i σ ixy ( 0 )σ ixy (t ) , (11)
V i

where ν ≈ 2. In the liquid state the thermal average is equal for all atoms. Thus

Cσ (t ) = ν σ ixy ( 0)σ ixy (t ) . (12)

We will show that C (t) ~ exp(-t/τM). For this purpose we compute the Laplace transform,
σ

% (ς ) = ∞ e−tς C (t ) dt .
LC (13)
σ ∫ σ0

Detailed derivation is given in Ref. 44. The result is

% (ς ) = τ a2 (ς )
LCσ 2
, (14)
−( pˆ r +4 r2 )
1 − a2 (ς ) e
where

1 ⎧⎪1 + τ (ς + 2iω ) + i 2 3 z ⎫⎪

a2 (ς ) = ln ⎨ ⎬ , (15)
i 4 3 z ⎩⎪1 + τ (ς + 2iω ) − i 2 3 z ⎪⎭

and z = στ = Δω/ω. Now using the polar coordinates in the complex plane,

ρ eiθ = 1 + τ Re (ς ) + i 2 3z , (16)

θ 2 3z
a2 (ς ) = , tan θ = . (17)
2 3z 1 + τ Re (ς )

Thus the solution critically depends on the value of z. If 2 3z ≥ π 2 ,

τM = τLC, (18)
whereas if 2 3z < π 2 ,

τ LC 2 3z
= 1− . (19)
τM tan 2 3z ( )
The value of z varies with temperature, and
π
z = zc = , (20)
4 3

9
defines the viscosity crossover temperature TA = T*. Above TA eq. (18) holds, whereas below TA
eq. (19) applies.

5. Interpreting the Results

5.1. Crossover condition
From eq. (19) the crossover condition is given by
Δω π
= ≈ 0.45 . (21)
ω c 4 3
The phonon frequency ω depends on volume through the Grüneisen formula,
d ln ω
=γ . (22)
d ln V
The Grüneisen constant is about 2 for many materials. Now for metallic systems with the
random close packed (DRP) structure the coordination number NC close to 12 (~ 4π [45]), the
volume strain, ε v = Δ ln V , for changing the coordination number NC by ½ is [33, 46]

ε vcrit = 0.11 , (23)

thus activation of anankeon which changes NC by unity will result in the volume strain of
2ε vcrit = 0.22 . Therefore the change in ω due to anankeon excitation is

Δω
= Δ ln ω = 2γε vcrit = 0.44 , (24)
ω
for γ = 2, quite close to the value in eq. (21). This agreement illustrates the reasonableness of the
result expressed in eq. (19).

5.2 Glass transition

At low temperatures below the crossover temperature atomic dynamics become more
correlated and cooperative. Therefore the anankeons become correlated, and the assumption of
random sequence which led to eq. (19) breaks down. For instance two atoms are surrounded by
a glassy solid, breaking of a bond creates strong stress field around the atoms which tries to
restore the bond. In other word unlike the liquid above the crossover the system now has a
memory and behaves like an anelastic solid. Consequently the effective value of z becomes
smaller. It is difficult to estimate how z varies with temperature, but it should go to zero at the

10
glass transition because the system is no longer dynamic in the experimental time-scale.
Therefore the overall change in ω due to localized anankeon is of the order of 1/N. For small
values of z,
⎛ ⎞
τM 2 3z ⎟ 1
= 1 ⎜1 − = + .... (25)
τ LC ⎜ tan 2 3z ⎟ 4 z 2
( ) ⎠
⎝
Thus τM diverges at Tg, as expected. Strictly speaking, therefore, Tg is the Kauzmann
temperature [47] rather than the glass transition temperature.

5.3 Fragility
Angell classified liquids into fragile and strong glasses, by plotting viscosity in the
logarithmic scale against Tg/T, the so-called Angell plot [1]. In a very strong glass, such as silica
glass, the Arrhenius temperature dependence persists well above the glass transition up to very
high temperatures. In our model this means z > zc up to high temperatures. This is consistent
with our model [46] in which the critical strain increases with decreasing NC. Whereas there is
no simple way to estimate the value of z, because the square of the phonon frequency is
proportional to the local elastic constant C which scales with NC, we may argue that,

Δω ΔC 1
z= ≈ ≈ . (26)
ω C NC
For NC = 4 we obtain z = 0.5, higher than the critical value zc. Because silicate has an open
structure cutting one bond does not affect other bonds even below TA. Thus the value of z
remains high through the supercooled state down to low temperatures, resulting in the Arrhenius
behavior of viscosity with no crossover to the super-Arrhenius behavior.

5.4 Comparison with simulation

Whereas it is difficult to calculate how z depends on temperature, it is possible to gain
some insight through the comparison of eq. (19) with the results of simulation in Ref. 14. We
found that scaling of z by
γ
z ⎛ 1 − t ⎞
1 − = ⎜ ⎟⎟ , (27)
zc ⎜⎝ 1 − t g ⎠

11
where t = T/T*, tg = Tg/T*, T* = 1.3 TA, γ = 4, of eq. (19) fits well to the simulation data as shown
in Fig. 1. Although the physical meaning of this scaling is unclear, this agreement suggests that
our model captures some features of the crossover phenomenon in spite of its simplicity. Here
T* > TA, but this merely reflects the ambiguity of defining TA from the viscosity data.

6. Conclusion
The origin of glass transition has long been debated, without satisfactory resolution.
Whereas many research works focus on the glass transition itself, it is equally important to
examine the crossover behavior of viscosity in a liquid at high temperatures. Below the
crossover temperature, TA, cooperative atomic dynamics leads to super-Arrhenius temperature
dependence of viscosity, culminating inevitably to the glass transition. In our view this
crossover occurs because of the competition between phonons and local configurational
fluctuations represented by the action of cutting or forming atomic connectivity, called
anankeons. In this article we propose a simplistic model of atomic dynamics in liquid, based on
the concept of dynamic fluctuations in local atomic connectivity (anankeons), to elucidate the
viscosity crossover phenomenon in the liquid phase. With this model it is possible to explain the
crossover from a simple liquid to cooperative liquid and the divergence of viscosity near the
glass transition temperature. The model is a mechanical analog of the Drude model for the
electric transport in metal.

Acknowledgment
JB was support by NSF grant #DMS-1160962. TE was supported by the U.S. Department of
Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division.

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Figure caption:
Figure 1. Plot of τM/τLC against T/TA, circles by simulations for various models from Ref. 14,
the line by eq. (19) with the temperature scaling of eq. (27).

Fig. 1

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Appendix I. The Delone Hypothesis and the Ergodic Paradox.
An instantaneous snapshot of the atomic arrangement can be described as a set of points
, representing the position of atomic nuclei. With a very good approximation is efficiently
described as a Delone set. Namely it is characterized by two length scales 0 < rR < 1 defined as
follows: (i) any open Euclidean ball of radius r contains at most one point of , (ii) any closed
Euclidean ball of radius R contains at least one point of . The first condition is equivalent to
having a minimum distance 2r between any pair of distinct atoms. The second condition is
equivalent to forbidding holes a diameter larger than 2R. However, the principles of Equilibrium
Statistical Mechanics and the ergodicity with respect to translations contradict such a hypothesis.
This is the content of the so-called Ergodicity Paradox [23]. This is because in the infinite
volume limit, the ergodic theorem implies that with probability one, given any ε > 0, somewhere
in the atomic configuration two atoms are at a distance shorter than ε. Similarly, with probability
one, given any ε > 0, somewhere in the atomic configuration there is a hole of size larger than
1/ε. However, such local arrangement are rare, so that dynamically there lifetime is so short that
they are unobservable. Hence restricting the atomic configurations to make up a Delone set is a
reasonable assumption called the Delone Hypothesis

Appendix 2. Voronoi Tiling, Delone Graphs and Local Topology.

Given a Delone set and a point x ∈ , the Voronoi cell V(x) is defined as the set of
points in space closer to x than to any other point in . V(x) can be shown to be the interior of a
convex polyhedron containing the open ball centered at x of radius r and contained in the ball
centered at x of radius R [21, 22]. The closure T(x) of the Voronoi cell is called a Voronoi tile.
Two such tiles can only intersect along a common face. In particular two Voronoi cells centered
at two distinct points of do not intersect. The entire space is covered by such tiles, so that the
family of Voronoi tiles constitute a tiling, the Voronoi tiling. The vertices of the Voronoi tiles
will be called Voronoi points. Their set * is usual called the dual lattice. For a generic atomic
configuration, a Voronoi point has not more than d + 1 atomic neighbors in space-dimension d (3
in the plane and 4 in the space). In particular, the Voronoi points are the center of a ball with d +
1 atoms on its boundary, a property called by Delone (who signed Delaunay) the “empty sphere
property" [11]. It means that it is at the intersection of d + 1 Voronoi tiles. The d + 1 atoms

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located at the center of those tiles are the vertices of a simplex (triangle for d = 2, tetrahedron for
d = 3) that generates the so-called Delaunay triangulation.
Two points x; y ∈ will be called nearest neighbors whenever their respective Voronoi
tiles are intersecting along a facet, namely a face of codimension 1. The pair {x, y} will be called
an edge. In practice, though, using physical criteria instead of a geometrical one, an edge might
be replaced by the concept of bond, to account for the fact that the atoms associates with x and y
are strongly bound [15, 20]. The term “strongly" is defined through a convention about the
binding energy, so as to neglect bonds between atoms weakly bound to each other. Whatever the
definition of an edge, geometrical or physical (bonds), this gives the Delone graph G = ( , ),
where plays the role of the vertices and denotes the set of edges or of bonds. At this point
the Delone graph needs not being oriented.
Along a graph, a path is an ordered finite set of edges, each sharing a vertex with its
successor or with its predecessor. The number of such edges is the length of the path. The graph-
distance between two vertices is the length of the shortest paths joining them. A graph-ball
centered at x of radius n will be the set of all vertices at graph distance at most n from x. Such
graph balls correspond to local clusters. Two graph balls are called isomorphic if there is a one-
to-one surjective map between their set of vertices, which preserve the graph distance. As a
result, if the atomic positions is slightly changed locally in space, the graph balls might still be
isomorphic. Therefore graph ball, modulo isomorphism are encoding what physicists called the
local topology
of the atomic configuration. The transition between two graph balls can be described precisely
through the concept of Pachner moves [21, 22, 24]. This concept was created by experts of
computational geometry, to describe the deformation of manifolds via a computer. A Pachner
moves can only occur if at least one Voronoi point becomes degenerate, namely it admits at least
d + 2 atomic neighbor at some point during the move. Such moves correspond to a local change
in a graph ball, namely an edge disappear another may reappear. A Pachner move corresponds
exactly to the concept of anankeon. It can be described through using the Delaunay triangulation
as explained in Fig. A1. A recent simulation [48] indeed show that the average number of atoms
involved in the saddle point (a mid-point of Pachner move) is five for d = 3.

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 Figure A1. Left: a Pachner move in the plane. Right: a Pachner move in the 3-space. In 3D-
space such a move involves at least five atoms moving quickly to deform the Delaunay
triangulation, changing the nature of the Delone graph, namely the local topology. This number
five has been seen in numerical simulations [48].

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