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Kumar Et Al 2022 Anomalous Heating in A Colloidal System
Kumar Et Al 2022 Anomalous Heating in A Colloidal System
Kumar Et Al 2022 Anomalous Heating in A Colloidal System
Edited by Christopher Jarzynski, Institute for Physical Science and Technology, Department of Chemistry & Biochemistry, Department of Physics, University
of Maryland, College Park, MD; received October 8, 2021; accepted December 20, 2021
We report anomalous heating in a colloidal system, an experi- heating has not previously been seen experimentally, neither in
mental observation of the inverse Mpemba effect, where for two systems that exhibited the anomalous cooling effect (10–16, 26,
initial temperatures lower than the temperature of the thermal 28–30) nor in any other system.
bath, the colder of the two systems heats up faster when cou- Here we present experimental evidence for the inverse
pled to the same thermal bath. For an overdamped, Brownian Mpemba effect. We also observe a strong version (31) of the
colloidal particle moving in a tilted double-well potential, we find effect, where, for a carefully chosen initial temperature, a system
a nonmonotonic dependence of the heating times on the initial heats up exponentially faster than systems that were initially
temperature of the system. Entropic effects make the inverse at different temperatures. Surprisingly, as we shall see, subtle
Mpemba effect generically weaker—harder to observe—than the differences between high- and low-temperature limits generically
usual Mpemba effect (anomalous cooling). We also observe a make the inverse effect more difficult to observe experimentally.
strong version of anomalous heating, where a cold system heats Moreover, the mechanism for the inverse effect that we find to
up exponentially faster than systems prepared under slightly be relevant in our experiments does not depend on the presence
different conditions. of metastability (32), which played a crucial role in the forward
cases explored in previous experiments.
inverse Mpemba effect | forward Mpemba effect | thermal relaxation |
Fokker–Planck equation | feedback traps
Experimental Setup
PHYSICS
In our experiment, a Brownian particle (silica bead, Ø1.5 μm)
cold temperature should then take longer to heat than a system olution (33, 34). Here we create a one-dimensional tilted double-
initially at a cool temperature. However, for rapid heating, a well potential U (x ) in a finite domain, with a very low barrier
system may evolve toward equilibrium so that its intermediate (Fig. 2) (Materials and Methods). The geometric asymmetry in
states are not in thermal equilibrium and are not characterized the potential is defined by the parameter α = |xmax /xmin |. Our
by a unique temperature. In such cases, the possibility of anoma- setup has steep walls at the domain boundaries corresponding
lously fast heating has recently been predicted and confirmed to the maximum force Fmax ≈ 20 pN ≈ 5 kB Tb /nm applied by
in numerical studies of an Ising antiferromagnet (1). Further the optical tweezers (Materials and Methods). The nearly vertical
numerical studies suggest that these effects may be seen in a wide walls confine particle motion to a box with size L ≡ xmax − xmin =
variety of systems, including fluids with inelastic (2–4) and elastic 240 nm and asymmetry α ≈ 2.
(5, 6) collisions and spin glasses (7).
Although anomalous heating is a recent prediction, an anal-
ogous anomaly for cooling and freezing has been noted in ob-
Significance
servations of water dating back to 350 BC (8). Its first systematic
study was done in 1969 by Mpemba and Osborne, who concluded
that hot water could begin to freeze in a time shorter than that A cold system normally takes longer to warm up than a cool
required for cold water (9). This phenomenon has since been system. Yet recent theoretical studies have suggested that the
dubbed the Mpemba effect and was followed up with further ex- reverse may sometimes be possible. Here, using a colloidal
periments on water (10–16), accompanied by some controversy, particle in a heat bath, we present experimental evidence for
tracing back to the difficulty of obtaining reproducible results (17, this inverse Mpemba effect. By carefully choosing the energy
18). Proposed mechanisms for the effect include evaporation (10, landscape, we can make the cold system heat up exponen-
19, 20), convection currents (21–23), dissolved gases and solutes tially faster than the heating rate of cool systems. While
(11, 14, 21), supercooling (12, 13), and hydrogen bonds (24, 25). similar behavior has been seen in systems that cool down—
In an effort to understand the Mpemba effect in more generic the Mpemba effect—we find that entropic effects generally
terms, Lu and Raz introduced a theoretical picture that related make anomalous heating harder to observe than anomalous
the effect to the geometry of system dynamics in a state space cooling.
whose elements are defined by the amplitudes of eigenmodes
of linear dynamical systems (1). A fast quench can then lead a Author contributions: J.B. designed research; A.K. performed research; A.K. and J.B.
system to follow a nonequilibrium path through state space to analyzed data; and A.K., R.C., and J.B. wrote the paper.
equilibrium that is shorter than the path traced out by a slowly The authors declare no competing interest.
cooling system. In recent work, we showed that this kind of This article is a PNAS Direct Submission.
Mpemba effect is present in a system consisting of a colloidal This article is distributed under Creative Commons Attribution-NonCommercial-
particle immersed in water and subject to a carefully designed NoDerivatives License 4.0 (CC BY-NC-ND).
potential (26). From this point of view, the dynamics of cooling 1
To whom correspondence may be addressed. Email: johnb@sfu.ca.
and heating obey similar principles, and anomalous heating rep- This article contains supporting information online at https://www.pnas.org/lookup/
resents an inverse Mpemba effect. Yet, despite a formal similarity suppl/doi:10.1073/pnas.2118484119/-/DCSupplemental.
between the cases of heating and cooling (1, 27), anomalous Published January 25, 2022.
FI Host
M L
532 nm L L
M
Trapping PBS
L
90 % AOD
L
M BS M
Detecon
10 %
SF SC L
HW
660 nm
M M
LED
MO
MO
M
DM
L CS
F Trapping
L beam beam
L Cam
M M
Fig. 1. Feedback trap based on optical tweezers. (A) Schematic of the feedback trap setup. FI, Faraday isolator; M, mirror; SF, spatial filter; BS, beam splitter
(nonpolarizing); L, lens; MO, microscope objective; SC, sample chamber; PBS, polarizing beam splitter; HW, half-wave plate; F, short-pass filter; QPD, quadrant
photodiode; DM, dichroic mirror; CS, cover slip; Cam, camera; FPGA, field-programmable gate array. Planes conjugate to the back focal plane of the trapping
objective are shown in red dashed lines. (Inset) An image of the cage system consisting of the trapping and detection objectives. (B) One cycle of a feedback
trap consists of three stages: (i) measurement of the current position of the particle, (ii) calculation of the force based on the potential (black) to be imposed,
and (iii) application of the force by shifting the trapping laser (green). Optical tweezers apply a linear restoring force, where k is the stiffness of the harmonic
trap and Δx is the expected trap displacement.
Experimental Protocol
D[p(x , t); π(x ; Tb )] ≡ dx |p(x , t) − π(x ; Tb )| ≡ D(t)
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The inverse Mpemba effect occurs if, for three different tempera-
tures Tcold < Tcool < Tb , the equilibration time tcold of an initially
Nb
cold system at temperature Tcold is smaller than the equilibra- ≈ |pi − πi | . [2]
tion time tcool of the initially cool system at temperature Tcool , i=1
when coupled to a common thermal bath at temperature Tb . To
study the effect, we impose an instantaneous heating quench in
our experiments via a three-step process: 1) prepare the initial Here pi ≡ p(xi , t) is the frequency estimate of the probability
state of the system corresponding to the Boltzmann distribu- for a measured position x at a time t in the interval [xi , xi+1 ),
tion π(x ; T0 ) ∝ exp[−U (x )/kB T0 ] at an initial temperature T0 , where xi ≡ xmin + (i − 1)Δx , with Δx = (xmax − xmin )/Nb and
2) release a particle at a position sampled from the initial distri- Nb the number of bins. Similarly, πi is the frequency estimate
bution π(x ; T0 ), and 3) record the trajectories of the particle as it of the Boltzmann distribution at Tb .
relaxes in a bath at temperature Tb . The initial positions are sam- We note that other choices of distance functions may have a
pled assuming U (x ) to have infinite potential walls at the domain more physical interpretation. For example, the Kullback–Leibler
boundaries. Once the particle is released into the bath, it is always (KL) divergence connects the nonequilibrium free energy of a
at the bath temperature. We repeat the quenching protocol N = system to the entropy produced during the relaxation process
5,000 times, with each cycle 60 ms long, to create a statistical (36–41). However, for analyzing our experiments, the L1 distance
ensemble of the state of the system at each time step Δt = 10 is simpler to evaluate and thus more convenient than the KL
μs. The dynamics of the particle after the quench in the potential divergence. Nevertheless, we confirm, as predicted in earlier
U (x ) can be described by the overdamped Langevin equation theoretical work (1), that the detection of the inverse Mpemba
1 2kB Tb
ẋ = − U (x ) + η(t), [1]
γ γ
where γ is the Stokes friction coefficient and η is Gaussian white
noise, with η(t) = 0 and η(t) η(t ) = δ(t − t ).
Although the initial and final states in our experiment obey
Boltzmann distributions at temperatures T0 and Tb , the interme-
diate states p(x , t) are not in equilibrium: they are not a Boltz-
mann distribution for any temperature T. For this reason, instead
of trying to define an intermediate effective temperature, we
measure the distance D between the intermediate state p(x , t)
and the equilibrium state π(x ; Tb ) (1, 26). From equivalent al-
ternatives (1), we choose the L1 distance (35) for the analysis of
particle trajectories in our experiments. This distance is defined Fig. 2. Schematic of the energy landscape U(x) used to explore the inverse
as the integrated absolute value of the difference between the Mpemba effect, set asymmetrically (α = 2) within a box [xmin , xmax ] with
densities p and π, potential walls with finite slope at the domain boundaries.
PHYSICS
Thus, we observe a sequence of normal, anomalous, and normal intuitively why the inverse Mpemba occurs in this system. At
regimes for relaxation to thermal equilibrium (Figs. 4 and 5). very low initial temperatures, the tilt in the potential leads to
a probability density of initial particle positions that is con-
Analysis in the High–Bath Temperature Limit centrated in the middle of the domain (i.e., within the lower
In Fig. 2, the variations in U0 (x ) throughout the domain well depicted in Fig. 2). At the high-temperature equilibrium, it
[xmin , xmax ] are kB Tb , implying that dynamics at the bath is approximately uniformly distributed throughout the domain.
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temperature approximate ordinary diffusion, i.e., Brownian Because the dynamics of the system in the bath are dominated
motion or Wiener process. To simplify the analysis of the by diffusion, most particles diffuse a distance that is typically ≈
relaxation trajectories in U (x ) at a finite temperature Tb , we L/4. At intermediate temperatures, the initial probability density
is split between the two well positions. A significant number
of particles in the left well will need to diffuse a distance ≈
L/2, implying an equilibration time ≈ [(L/2)/(L/4)]2 = 4 times
longer. Indeed, Fig. 4 shows that the equilibration time at a
cold temperature can be roughly four times faster than that at
intermediate temperatures (40 ms/10 ms = 4).
In the high-temperature approximation, the Fokker–Planck
equation describing the probability density p(x , t) of particle
positions reduces to the heat equation,
∂p 1 ∂ kB Tb ∂ 2
= − U (x ) + p(x , t)
∂t γ ∂x γ ∂x 2
kB Tb ∂ 2 p
≈ ≡ Lfree p, [3]
γ ∂x 2
subject to no-flux boundary conditions at x = {xmin , xmax }, where
Lfree is the Fokker–Planck operator for a freely diffusing particle
(U (x ) = 0). Note that this high-noise limit is complementary
, [7] quench for the case of a heat bath whose average energy greatly
Z L exceeded the range of potential variation. We used this feature to
where Z is the normalization constant, defined such that model system dynamics in a high–bath temperature limit where
vk |vk = 1 with k = 1, 2, · · · . the relaxation dynamics are governed by a simple heat diffusion
Since anomalous heating (inverse Mpemba) is associated with equation. Using numerical integrals of analytic expressions for
a2 coefficients where |a2 (Tcool )| > |a2 (Tcold )| for cool and cold the eigenfunctions, we obtained the a2 coefficients as a function
temperatures, respectively, a nonmonotonic temperature depen- of initial temperature. We found evidence for the strong inverse
dence of the a2 coefficients leads to anomalous heating effects. Mpemba effect, special temperatures where the systems heat up
However, these coefficients are not directly accessible in exper- exponentially faster than those at other initial temperatures.
iments. Instead, we extract them from decay curves of the dis- One interesting feature of our system is that it shows that
tance function D(t) defined in Eq. 2. Measuring differences ΔD the inverse Mpemba effect can be observed in a system where
between the initial distance and noise-limited final distance gives metastability does not play an important role. Indeed, although
a quantity proportional to |a2 | (26). We measure this difference our potential has two wells, we can accurately model dynamics
as a function of initial temperature. in the bath state using an infinite-temperature approximation,
Fig. 6 shows the nonmonotonic temperature dependence of where the potential is flat and the motion is purely diffusive. In
ΔD. The ΔD values correlate with the measured equilibration this case, the form of the potential is important only for defining
times. To see the agreement of the measured values of ΔD for the low-temperature probability densities for the system state. After
the quench, it plays no role. By contrast, most scenarios explored
previously for continuous-state systems for the forward Mpemba
effect depend on the slow time scales corresponding to barrier
hopping at low temperature (32). Note, however, that a recent
study predicts the forward Mpemba effect in potentials with a
single well (47).
Previous experiments on the forward Mpemba effect showed a
clear separation of the time scales determined by the eigenvalues
λ2 and λ3 (26). We can offer some insight as to why it is easier
to observe the forward Mpemba effect than the inverse effect:
when a system relaxes to a bath at temperature Tb , the time scale
separation between the decay curves corresponding to λ3 and
λ2 depends on the ratio Λ = λ3 /λ2 . In particular, in order to
measure the ΔD values, one fits the part of the decay curve that
Fig. 6. Measurements of decay amplitude ΔD for different initial tempera-
tures T0 . Markers denote experimental measurements, and the solid red line
corresponds to λ2 . Thus, the greater the value Λ, the easier the
is based on the |ΔD| values calculated from the Fokker-Planck equation in accurate measurement of the ΔD values.
the high-temperature limit. The arrow indicates the temperature at which For the forward Mpemba effect studied in ref. 26, the sys-
the strong inverse Mpemba effect occurs. Error bars represent 1 SD and are tem cools from a hot temperature to a cold temperature in a
calculated from the fits. double-well potential, and the ratio Λ of eigenvalues λ3 to λ2
PHYSICS
are statistically similar to results for the forward case obtained ⎨ max
with only 1,000 trajectories. U(x) ≡ U0 (x) xmin ≤ x ≤ xmax [8]
⎪
⎪
⎩ F x
Are these general features of Λfor and Λinv , or are they special max x > xmax ,
to our potential? Since the dynamics of a2 (t) correspond to hops
over the barrier, we expect that the ratio of eigenvalues λ3 to where U0 (x) is given by
λ2 depends on the barrier height Eb as Λfor ∼ exp[Eb /kB Tb ] 1,
1
2 2
(1 − x ) − x ,
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