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According to thermodynamics, different forms of work between the two states will typically follow a preferred
can be transformed into one another, with an efficiency of pathway that connects these states via the lowest lying
at most 100% [1]. This lossless limit is achieved with a saddle point, the so-called activated state. One can pro-
reversible process, i.e., an infinitely slow process. The ject the motion on this pathway and introduce a one-
corresponding power output is therefore zero and thus of dimensional reaction coordinate x with corresponding
limited interest from a practical standpoint. One of the effective free energy potential U0 x. The two rest states
early discussions about efficiency at finite power is attrib- of the machine, that is, the minima in the absence of
uted to Moritz von Jacobi around 1840. He realized that the external forces, correspond to, say, locations x 0 and
output power of an electrical device operating in the linear x L. The activated state lies at an intermediate position
response regime is maximum when the internal and exter- xa L, 0 1. In the unperturbed phase there are no
nal resistors are the same, yielding an efficiency of 50%. net transitions, and the states 1 and 2 have the same base-
The Jacobi theorem can easily be reproduced in the much line potential value, U0 0 U0 L 0. The potential has
more general context of linear irreversible thermodynam- a maximum Ua U0 L at the activated state, whose
ics: in any engine operating in the linear response regime, value is typically much larger than the thermal energy
maximum power is achieved when the loading force is 1 kB T (T being the temperature and kB the
equal to half of the stopping force; the corresponding Boltzmann constant). In this rest state, the rates, k0 from
efficiency (output power over input power) is equal to 1 to 2 and k 0 from 2 to 1, are equal and given by an
1=2. A similar result has been proven for the transforma- Arrhenius law, k 0 k k expU . We as-
0 0 a
tion of heat into work, where the maximum efficiency, the sume a constant preexponential factor .
Carnot efficiency, is again achieved under reversible op- In the operational regime, that is, in the presence of
eration, with zero power output. In the regime of linear external forces, states 1 and 2 can be identified as fuel
response the efficiency at maximum power is again 50% of (or reactant) and product states, respectively. To
the Carnot efficiency [2]. More recently, in this latter case transform fuel into product, the machine is subject to a
various explicit results, including bounds for efficiency at driving force F1 which allows it to overcome an opposing
maximum power, have also been obtained in the nonlinear but weaker loading force F2 , F2 F1 . These forces can
regime [311]. Whether similar results can be obtained for be of various physical origins, including chemical (differ-
isothermal machines has been recently questioned in [12]. ences in chemical potentials), electrical (internal or exter-
In the present Letter we show that this is in fact the case. nal electric fields), or mechanical (e.g., optical tweezers,
In particular, we derive upper and lower bounds for atomic force microscope, or optical rotational torque). The
the efficiency at maximum power, and we show that the
coefficient of the quadratic term in an expansion around
equilibrium vanishes for systems possessing left-right
symmetry.
Generic model for a molecular motor.We first consider
a generic model for a molecular motor, namely, a two-state
machine operating along a one-dimensional reaction coor-
dinate, see Fig. 1. The states correspond to two minima of
an appropriate free energy landscape. While a physical FIG. 1. Schematic free energy potential U0 x for a two-state
energy landscape is expected to be very complicated molecular engine described by a reaction coordinate x under the
and high dimensional, the thermally activated transitions net load force F F1 F2 0.
combined effect of driving and loading is a tilting of the irreversible thermodynamics of efficiency at maximum
potential towards the product state 2, Ux U0 x Fx, power equal to 1=2. The associated relation between the
with F F1 F2 0. In a transition from state 1 to state forces, 2F2 F1 is obtained from the first term in expan-
2, a (scaled) input energy 1 F1 L is transformed into a sion (3), 2 1 2 .
(scaled) output energy 2 F2 L. The efficiency of this Turning to the next order corrections in Eqs. (3) and (5),
transformation is given by the coefficients vanish in the symmetric case 1=2,
2 F2 reminiscent of a similar property for thermal machines
: (1) [10]. Note also that the coefficient of the term proportional
1 F1 to in (5) goes from a maximum value 1=8 at 0 to the
Equation (1) quantifies how efficiently the energy spent on minimum value 1=8 for 1, switching from positive
driving the system is utilized in the process of doing work to negative values at 1=2, again reminiscent of an
against the load. Its maximum value, 1, is reached analogous feature in thermal machines [11]. Note that the
when the loading force F2 approaches the driving force F1 , first two terms of the expansion (5) were also derived in
and the transition from 1 to 2 becomes infinitely slow. In [12], while the relevance of the parameter was pointed
this reversible lossless limit the power vanishes. out in [14].
In the case of finite and, in particular, of maximum The efficiency ? at maximum power is a function of
power, the location of the activated state plays a crucial and . One easily verifies that ? is a monotonically
role. For a so-called Eyring-like process [13] the activated decreasing function of for given 0. The upper limit
state is very close to the fuel state 1; i.e., is close to zero. is the efficiency ?E ? 0; 1 of the extreme Eyring-
The perturbation Fx barely affects the height of the like scenario, and the lower limit is the efficiency 0
activation barrier that needs to be crossed to go from state ? 1; ?K of the extreme Kramers-like case:
1 to 2. The rate also remains essentially unaffected,
k k0 . However, a maximum barrier increase of FL 1 e 1 e
?K ? ?E : (6)
occurs for the backward transition, resulting in a rate k 1e 1 e e
k0 expFL (assuming FL Ua ). On the other
hand, in the Kramers-like scenario 1 [13], k We next consider the dependence, starting with the
k0 expFL, while k k0 remains essentially unaf- variation of the bounds. The Eyring-like efficiency E
fected. More generally, for a barrier at xa L, one has increases monotonically from 1=2 when ! 0 to E
k k0 exp and k k0 exp1 , where 1 when ! 1. The Kramers-like efficiency K decreases
1 2 FL is the net energy loss or net load. F is monotonically from 1=2 when ! 0 to K 0 when
a proper thermodynamic force (net force divided by the ! 1. The variation of between these bounds depends
temperature) that appears in the entropy production and is on . When 1=2, decreases monotonically from
thus a measure of the distance from equilibrium [1]. 1=2 when 0 to 0 when ! 1. The system is in the
With these explicit expressions for the rates, we turn to product regime (Kramers-like), and behaves much like
the output power given by the output energy 2 multi- the Kramers-like limit, never rising above the linear re-
plied by its net rate of production, k2 , with k sponse value 1=2 [dotted curve, short-dashed curve, and
k k k k0 e e1 . To specify the con- filled circles in Fig. 2(a)]. On the other hand, when 0 <
dition of maximum power we set @=@2 0, which 1=2 the system is in the fuel regime (Eyring-like), and
yields the unique solution starts at 1=2 when 0, rises to a unique maximum,
and then decreases to 0 as ! 1 [long-dashed curve, solid
1 e curve, and open circles in Fig. 2(a)]. The optimal value
2 (2)
1 e e of the efficiency at maximum power occurs at the net load
value which solves the transcendental equation obtained
1 1 by setting the derivative of (4) with respect to equal to
2 2 3 O4 : (3) zero, 1 e 1 e 1 e
. Each point along the
2 6
curve in the inset of Fig. 2(a) is associated with a different
This result in Eq. (1) yields one of the central results of this value of . High efficiencies at maximum power require the
Letter, namely, the efficiency at maximum power: system to operate very near the fuel state. Thus, for in-
e 1 stance, referring to the figure, the maximum of the 0:1
? (4) curve (solid) is 0:69 and occurs when the net load is
1e 1
3:19. A maximum efficiency of say 0:9 requires
1 1 2 1 12 122 2 that the net load be 5:68 and that the motor operate at
O3 : (5) 0:016.
2 8 96 We can repeat our analysis for 0, with net transi-
We point to a number of revealing observations. The tions going from state 2 to state 1. Indeed, many motors,
first term of the expansion (5) is the prediction of linear including ATPase, can operate in reverse. The interchange
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PRL 108, 210602 (2012) PHYSICAL REVIEW LETTERS 25 MAY 2012
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PRL 108, 210602 (2012) PHYSICAL REVIEW LETTERS 25 MAY 2012
1 ZL ZL
In n2
dxeU0 x dyyn eU0 xy : (12) [1] H. B. Callen, Thermodynamics and an Introduction
n!L 0 0
to Thermostatistics (Wiley, New York, 1985), 2nd ed.
[2] C. Van den Broeck, Phys. Rev. Lett. 95, 190602
Since 0 I1 I0 , the coefficient a2 =4a1 I1 =I0 (2005).
1=2=4 of the linear term lies between 1=8 and 1=8, as [3] F. Curzon and B. Ahlborn, Am. J. Phys. 43, 22 (1975).
was the case for the 2-state model, see Eq. (5). [4] T. Schmiedl and U. Seifert, Europhys. Lett. 81, 20003
Furthermore, the coefficient is zero for a potential with (2008).
left-right symmetry, that is, when there exists a point x0 for [5] Z. C. Tu, J. Phys. A 41, 312003 (2008).
which U0 x x0 U0 x0 x. [6] A. E. Allahverdyan, R. S. Johal, and G. Mahler, Phys. Rev.
To proceed further, it is in general necessary to invoke E 77, 041118 (2008).
numerical calculations because the integrals in (10) cannot [7] Y. Izumida and K. Okuda, Europhys. Lett. 83, 60003
be performed analytically for a general potential U0 x. (2008).
[8] M. Esposito, K. Lindenberg and C. Van den Broeck,
However, analytic results can be obtained in some limits
Europhys. Lett. 85, 60010 (2009).
(such as the dominant high maximum case considered [9] M. Esposito, R. Kawai, K. Lindenberg, and C. Van den
above), or for some specific shapes of the potential. Broeck, Phys. Rev. E 81, 041106 (2010).
Examples include the square well, U0 x Ua , x 2 [10] M. Esposito, K. Lindenberg, and C. Van den Broeck, Phys.
0; L modulo L, and U0 x 0, x 2 L; L modulo Rev. Lett. 102, 130602 (2009).
L, and a sawtooth potential. To illustrate, we quote the [11] M. Esposito, R. Kawai, K. Lindenberg, and C. Van den
efficiency at maximum power for the square-well potential, Broeck, Phys. Rev. Lett. 105, 150603 (2010).
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PRL 108, 210602 (2012) PHYSICAL REVIEW LETTERS 25 MAY 2012
[12] U. Seifert, Phys. Rev. Lett. 106, 020601 (2011). [16] P. Reimann, Phys. Rep. 361, 57 (2002).
[13] J. Howard, Mechanics of Motor Proteins and the [17] R. L. Stratonovich, Topics in the Theory of Random Noise
Cytoskeleton (Sinauer Associates, Sunderland, MA, (Gordon and Breach, New York, 1963), Vol. 1.
2001). [18] C. Van den Broeck, N. Kumar, and K. Lindenberg (to be
[14] T. Schmiedl and U. Seifert, Europhys. Lett. 83, 30005 published).
(2008). [19] N. Golubeva, A. Imparato, and L. Peliti, Europhys. Lett.
[15] O. K. Dudko, T. G. W. Graham, and R. B. Best, Phys. Rev. 97, 60005 (2012).
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