Recent and earlier research
discussed in representative
publications
Long-standing melting problem
and theory of melting
There has been a long-standing
problem in understanding basic states of matter: solids,
liquids and gases. These states are understood on the
basis of the pressure-temperature phase diagram where
different states are separated from each other by phase
transition lines. Two of these lines, the solid-gas and
liquid-gas lines, were understood and their functional
form was worked out long ago. The third line, the
solid-liquid melting line, has remained completely
mysterious. It is interesting that in this age of
scientific and technological development, something as
basic as theoretical understanding of the
pressure-temperature dependence of the melting line was
still absent.
There are at least two reasons
why it is important to solve the melting problem. The
first is related to fundamental science and fundamental
understanding of the basic states of matter. We can’t
understand these states if we don’t know where the
melting line is on the phase diagram. The second reason
is related to applications: predicting phase diagrams is
the key area in materials science. There is an active
search for new functional and high-performance materials
(eg “Materials genome” project in the US), but in order
to predict the stability range of a new material we need
to be able to predict its melting point and its melting
line. This includes new advanced materials with tailored
properties in areas such as drug development and areas
where high-performance materials (used in, for example,
energy, environmental and space applications) are
subject to high pressure and temperature. Knowing the
functional form of the melting line immediately tells us
up to what temperature the system remains as a solid
before it melts.
In order to solve the melting
problem, one needs to solve the Clausius-Clapeyron (CC)
equation written in 1834 and about 200 years ago. This
was done for the solid-gas and liquid-gas lines long ago
because solid-gas and liquid-gas transitions involve the
gas state which is uncondensed and has no cohesion
energy. This greatly simplifies the solution of the CC
equation because the latent heat involved in the
solid-gas and liquid-gas transitions is related to the
energy of cohesion in a condensed phase (solid or
liquid). This simplification does not apply to the
melting line because both solids and liquids are
condensed states. So in order to solve the CC equation,
we need to explicitly know the equation governing liquid
thermodynamic properties in general form as well as the
liquid equation of state. And this problem of liquid
theory was exactly the reason why the melting problem
remained unsolved for 200 years.
Many physics luminaries
(Brillouin, Frenkel etc) worked on the melting problem,
including Nobel-prize laureates such as Born. In order
to solve the CC equation, one needs to know another
equation: the equation for liquid thermodynamic
properties such as entropy. And another group of physics
luminaries and Nobel laureates among them (Landau,
Lifshitz and Pitaevskii) have stated that deriving this
equation for liquid properties in general form is
impossible. If this is true then solving the melting
problem is also impossible.
Over a few years, me and my
collaborators thought hard and developed a new
understanding of the liquid state. This has given us an
advantage in solving the melting problem. I realised
that differentiating the CC equation and using the
similarity of specific heats of solids and liquids close
to melting (this similarity is backed up by our recent
theory of liquids and numerous experiments) gives a new
melting equation that can be solved.
The solution (Physical
Review E 2024) gives the first important result:
the analytical function of the melting line turns out to
have a simple quadratic, parabolic, form: pressure
depends on temperature quadratically along the melting
line. Second, it turns out that the parameters of this
parabola are governed by fundamental physical constants:
the Planck constant and electron charge and mass.
Therefore, all melting lines have this fundamental unity
of properties. These two results are confirmed by
experimental melting lines in several different types of
liquids, including noble, molecular, network and
metallic.
Properties of condensed matter and fundamental
physical constants
Liquid viscosity is strongly
system-dependent and also depends on temperature and
pressure. It is not possible to calculate liquid
viscosity in general form due to strong interactions,
the same problem that exists for liquid thermodynamics
(see below). It turns out that liquid viscosity at its
minimum is universal. We have recently shown how
fundamental physical constants provide the lower bound
of liquid viscosity (Science
Advances 2020). This minimal viscosity is a new
quantum property, featuring the Planck constant.
Interestingly, EM Purcell noted
that "the viscosities have a big range but they stop at
the same place" (Am. J. Phys., 1977), adding that he
does not understand this and that Weisskopf has
explained it to him (we didn't find this Weisskopf's
explanation). Our results provide the answer to this
question (Physics
Today 2021).
It turns out that the same
theoretical minimum for viscosity in terms of
fundamental constants applies to a very different
property: thermal conductivity and thermal diffusivity (Physical
Review B 2021). Fundamental constants also govern
the maximal velocity gradient that can be set up by a
biochemical machine in cells using chemical energy (Science
Advances 2023).
We have similarly applied our
ideas to relate another property, the speed of sound in
condensed matter phases to fundamental physical
constants. We have found (Science
Advances 2020) that fundamental constants give the
upper bound to the speed of sound in solids and liquids
of about 36 km/s. The ratio of this bound to the speed
of light depends only on two important dimensionless
constants, the fine structure constant and the
proton-to-electron mass ratio.
Having realised that several
other important properties of condensed matter are
governed by fundamental physical constants, I have
written a review of this topic (Advances
in Physics 2023).
Theory of liquid thermodynamics
One
of the triumphs of physics has been the theory of solid
state developed at the beginning of the last century.
This provided a fundamental understanding of the basic
properties of solid matter such as the ability to absorb
and transfer heat. Solid state theory was preceded by
the equally successful theory of gases. But when we turn
to the third main phase of matter, the liquid phase,
most textbooks remain silent about the most basic liquid
properties such as heat capacity. Paradoxical though it
may seem in this age of scientific and technological
advancement, we still do not understand the most basic
aspects of liquid behaviour. The combination of strong
interactions with large atomic rearrangements has proved
to be the ultimate obstacle to developing a theory of
liquids. This was famously summarized as the "no small
parameter" problem (eg by Pitaevskii). Landau and
Lifshitz repeatedly assert that liquid energy and heat
capacity can not be calculated in general form, contrary
to solids and gases (Statistical Physics, Pergamon
Press, 1969, par. 66 and par. 74). I have proposed that
contrary to this statement, liquid energy and heat
capacity can in fact be calculated and understood.
The argument of Landau,
Lifshitz and Pitaevskii concerns the approach to liquids
in which the interaction energy is calculated in
addition to the gas kinetic energy, as an integral over
interatomic potentials and correlations functions. This
general approach formed the basis for previous theories
of liquids. Apart from the problem of being
system-specific as discussed by L&L, there are other
important disadvantages of this approach: (a)
interatomic potentials and correlations functions are
not generally available, consequently, apart from very
simple and exotic liquids such as those composed of
noble elements, it has not been possible to calculate
liquid energy and heat capacity; (b) calculations become
difficult beyond simple cases and approximations
difficult to control; (c) it is not easy to see how the
results are consistent with large experimental decrease
of liquid heat capacity over a wide temperature range.
Together with collaborators, I
have developed theory of liquids based on excitations,
phonons. Differently from solids where the number of
phonons is fixed to 3N, this number is variable in
liquids and reduces with temperature. This addresses the
problem set out by Landau, Lifshitz and Pitaevskii:
there is in fact a small parameter in the liquid theory,
but this parameter operates in a variable phase space.
This gives the key to liquid theory, as discussed in my
book (Cambridge
University Press, 2023). This theory for the first
time explains a wide range of experimental data in many
real liquids, including their specific heats.
"The most detailed and rigorous
test of the phonon theory of thermodynamics" was
undertaken (J Proctor, Physics of Fluids 2020 and book
on liquid and supercritical states 2020 and Proctor's
book ). Proctor notes that the theory is falsifiable but
tests did not falsify it.
A new
line on a phase diagram of matter above the
critical point: the Frenkel line
According to previous
textbook understanding, no differences can be made
between a gas and a liquid above the critical point, an
abrupt terminus of the liquid-gas coexisting line.
Recently, we have discovered that this is not the case,
and that the phase diagram of matter should be modified.
We have proposed that a new line ("Frenkel line") exists
on the phase diagram above the critical point at
arbitrarily high pressure and temperature, and which
separates two physically distinct states of matter.
Crossing the line corresponds to qualitative changes of
physical properties of the system.
The Frenkel line has been since
experimentally confirmed in supercritical Ne, CH4,
CO2, N2, C2H6
and H2O using X-ray, neutron and Raman
scattering. We have written a review discussing this
evidence (Physics
Reports 2021).
Field
theory of liquids and dissipation effects
I have proposed a Lagrangian
theory of liquid dynamics involving two scalar fields.
Dissipation was believed to be hard to describe by a
Lagrangian, however in my theory the energy dissipated
by one field is taken up by the second field (Physics
Reports 2020, Physical
Review D 2020). The theory results in gapped
momentum states (GMS), the effect which we now realize
extends beyond liquids and into other areas such as
plasma, holographic models, relativistic hydrodynamics
and so on.
The problem of glass transition
The problem of glass
transition was considered as one of the deepest and most
interesting challenges in physics. The problem consists
of two parts, dynamic and thermodynamic. The
thermodynamic part of the problem of glass transition is
related to two widely observed experimental facts: (a)
heat capacity changes with a jump at the glass
transition temperature Tg, and (b) no distinct solid
glass phase has been identified experimentally or
suggested theoretically. Therefore, the problem is to
explain the jump of heat capacity without asserting the
existence of a distinct solid glass phase. This
problem is also common to other disordered systems,
including spin glasses. I have proposed that if, as is
the case, Tg is defined as the temperature at which the
liquid stops relaxing at the experimental time scale,
the jump of heat capacity at Tg follows as a necessary
consequence due to the change of system's elastic,
vibrational and thermal properties. The resulting
equations have no fitting parameters, and compare well
with experimental results. This theory explains widely
observed time-dependent effects of glass transition,
including logarithmic increase of Tg with the quench
rate, and identifies three distinct regimes of
relaxation (Physical
Review B, 2011)
The dynamic part of the problem
of glass transition is to explain the physical origin of
several famous relaxation laws and dynamic effects that
liquids show in the glass transformation range: the
Vogel-Fulcher-Tammann law, stretched-exponential
relaxation, dynamic crossovers etc. These phenomena are
universal and are seen in other systems as well (e.g.
spin glasses), yet their physical origin is not
understood. I have proposed a solution to this problem
based on elastic interactions in a liquid. The solution
is based on a non-trivial way in which high-frequency
elastic waves propagate in a liquid. Crucially, the
propagation range of these waves increases with liquid
viscosity. This is in contrast to frequently discussed
hydrodynamic waves, whose propagation range decreases
with viscosity.
Radiation damage
Radiation damage is a large and
important area in science and technology, and has
far-reaching consequences for materials performance in a
wide range of applications, including immobilization of
nuclear waste and future fusion reactors. This
performance crucially depends on whether a material is
amorphizable by radiation damage or is able to recover
back to crystal. The phenomenon of resistance to
amorphization by radiation damage remains largely not
understood from theoretical standpoint. I elucidated the
phenomenon of resistance to amorphization by radiation
damage using massive parallel molecular dynamics
simulations. This was supported by quantum-mechanical
calculations of electronic structure.
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