REPORTS coherence allows us to break detailed balance

Extracting Work from a Single between emission and absorption as in the case
of LWI (Fig. 1, D and E). The connection with

Heat Bath via Vanishing Maxwell’s demon is clear. In (8) we trade in

quantum information (negentropy) to get useful

Quantum Coherence
work as we increase overall entropy. With
phaseonium fuel, we get a kind of “sorting
action” in which hot atoms emit photons, but
Marlan O. Scully,1,2 M. Suhail Zubairy,1,3 Girish S. Agarwal,1,4 cold atoms absorb less than they ordinarily
Herbert Walther2 would. Phaseonium fuel uses quantum coher-
ence and interference to achieve single bath
We present here a quantum Carnot engine in which the atoms in the heat bath operation in the spirit of Maxwell’s demon.
are given a small bit of quantum coherence. The induced quantum coherence Here, we do not claim to have a “perpetual
becomes vanishingly small in the high-temperature limit at which we operate mobile of the second kind.” We do claim to
and the heat bath is essentially thermal. However, the phase ␾, associated with be able to extract work from a single heat
the atomic coherence, provides a new control parameter that can be varied to bath. It takes energy, e.g., from an external
increase the temperature of the radiation field and to extract work from a single source of microwaves, to prepare the coher-

Downloaded from https://www.science.org at Chalmers University of Technology on December 03, 2021

heat bath. The deep physics behind the second law of thermodynamics is not
violated; nevertheless, the quantum Carnot engine has certain features that are
not possible in a classical engine.
Carnot showed that every heat engine has the
same maximum efficiency, determined only
by the temperatures of the high-temperature
energy source at Th and the low-temperature
entropy sink at Tc (1). Specifically, the Car-
not efficiency for converting heat into work is
given by ␩ ⫽ 1 ⫺ Tc/Th. It follows that no
work can be extracted from a single heat bath
when Tc ⫽ Th.
Here, we propose and analyze a new kind of
quantum Carnot engine powered by a special
quantum heat bath, which allows us to extract
work from a single thermal reservoir. In this
heat engine, radiation pressure drives the piston.
Thus the radiation is the working fluid (analo-
gous to steam), which is heated by a beam of
hot atoms (analogous to coal) (Fig. 1).
The temperature of the radiation “work-
ing fluid” is determined by hot bath atoms,
which are resonant with the field, and by
flow through the cavity. When powered by
the regular (two-level) thermal atoms (Fig.
1B), the engine efficiency is given by the
Carnot limit. However, when the heat bath
consists of hot (three-level) atoms that have
a small amount of coherence between the
two nearly degenerate lower levels, things
are very different.
It has been noted that such an ensemble of
atoms constitutes a new state of matter, appro-
priately called “phaseonium” (2), that makes
possible, for example, lasing without inversion
(LWI) (3). We show here how the use of quan-
tum coherence fundamentally alters quantum
heat engine (QHE) operation. In the photon
1
Department of Physics and Institute for Quantum
Studies, Texas A&M University, TX 77843, USA. 2Max-
Planck-Institut für Quantenoptik, D-85748 Garching,
Germany. 3Department of Electronics, Quaid-i-Azam
University, Islamabad, Pakistan. 4Physical Research
Laboratory, Navrangpura, Ahmedabad-380009, India.
Carnot QHE (Fig. 1A), Th, Tc, and ␾ (the
atomic phase) are control parameters, and the
efficiency of converting heat to work is given
by ␩␾ (Fig. 1C). Thus, by the proper choice of
␾, work is obtained even when Th ⫽ Tc, i.e.,
even when there is only one thermal bath.
There is an interesting connection between
this result and the demon suggested by Maxwell
(4) and recently demonstrated in an elegant
experiment by Linke et al. (5). This demon
could sort hot atoms from cold and, therefore,
could obtain work from a single heat bath. At
first, this would seem to violate the second law,
and there was much discussion and confusion
on the subject for the next half-century. Then
Szilard (6) made the important contribution of
devising a “single-atom heat engine” that ex-
tracted work from one bath by using (classical)
information about the atom. He thought, incor-
rectly, that it was the acquisition of information
(about the atom’s position) that costs energy and
saves the second law. It was left to Bennett and
Landauer (4) to show that it was not the act of
measurement but rather the process of preparing
the system to make the measurement that was
thermodynamically costly. From their point of
view, exorcising the demon was a problem
solved by (classical) information theory.
In a recent paper (7), we used a Stern-
Gerlach apparatus to sort hot spins from cold
ones, thus acting as a sort of quantum Max-
well’s demon. To achieve cyclic operation, we
prepared the atomic center of mass in a well-
defined state and used this source of (quantum)
negentropy to extract work from a single bath.
Moreover, it was shown that the cost of prepar-
ing the center of mass wave packet was enough
to “preserve” the second law.
Here, we get work from a single bath by
using quantum coherence instead of quantum
negentropy. This is possible because quantum
ence, but we may view this energy as part of
the refining process yielding “superoctane”
quantum fuel. Surely the “price at the pump”
of phaseonium is higher than regular fuel, but
once the tank is full, a little quantum coher-
ence allows our QHE to extract energy from
the high-temperature heat bath more effi-
ciently, to run faster, or to do both.
Alternatively, we could incorporate the mi-
crowave generator (which produces the coher-
ence) into the photo-Carnot engine as a kind of
“quantum supercharger.” This approach comes
closer to our recent conclusions on the quantum
afterburner (8). In (8), we proposed and ana-
lyzed a toy laser–Otto cycle engine hybrid in
which we used laser physics to improve engine
efficiency. Here, we use insights gleaned from
LWI studies to improve the operating character-
istics of the photo-Carnot quantum heat engine.
The overall operating efficiency of the quantum
supercharger photo-Carnot engine will be ana-
lyzed in detail elsewhere (9).
Various interesting aspects of phaseonium
fuel are also discussed elsewhere (10–12).
For example, the phase coherence comes at a
cost. However, it can be (and often is) very
long lived. Thus, it is possible that the atomic
coherence could be produced during a period
of “low power demand,” stored, and used
later as desired.
Consider another interesting example of
phaseonium fuel. Suppose we want to in-
crease the power output of a classical Carnot
engine. That would be easily obtained with a
hotter fuel and an increase in Th. But what if
the walls of the heat bath melt down for
temperature higher than Th? And suppose Tc
is as low as reasonably possible? Then, we
would be stuck. However, with phaseonium
fuel the heat bath may be held at Tc while the
working ( photon) fluid is hotter than Th,
allowing us to coax a little more power from
the quantum engine.
The practicality and utility of the photo-
Carnot engine are not the problem here. But

862 7 FEBRUARY 2003 VOL 299 SCIENCE www.sciencemag.org


because phaseonium is different from freon and
steam, a new, variable ␾ is now available.
There is a useful connection to be made
with the work of Ramsey (13), who showed
that Kelvin-Planck statement of the second
law had to be extended when negative tem-
peratures were included for quantum me-
chanical spin 1/2 systems. We too find that
quantum coherence allows us to extend Car-
not’s famous result and obtain work from a
single reservoir.
The quantum heat engine concept was orig-
inally introduced in connection with the maser
(14) and was extended in many interesting later
works (15). Recent studies on the quantum
Carnot cycle are given in (16, 17), especially
cavity volume, ⍀ ⫽ S␲c/L is the frequency
for a cavity of length L where S is an integer,
and n៮ is the average number of thermal pho-
tons in the mode (21).
Thus the rate of change of average photon
number, n៮ ␾, generated by phased three-level
( phaseonium) atoms, is
nថ ␾ ⫽ ␣[2P a (n៮ ␾ ⫹ 1) ⫺ 共 P b ⫹ P c )(1⫹εcos␾)៮n ␾]
(2)
where ␣ is a simple rate factor, ε, is propor-
tional to the magnitude of atomic coherence
in the lower atomic levels b and c, and Pa, Pb,
and Pc are the thermal Boltzmann factors for
the levels a, b, and c, respectively.
REPORTS
preparing the coherence so that ␾ ⫽ ␲, the
radiation temperature is T␲ ⫽ Th(1 ⫹ n̄ε).
Hence, for large enough n៮ the temperature
difference T␲ ⫺ Th can be applicable even for
very small ε.
To substantiate the preceding heuristic
analysis and to determine ε, etc., we pro-
ceeded to sketch the density matrix and
thermodynamic analysis. As shown in (10–
12), Eq. 4 can be derived from an extension
of the quantum theory of a laser without
inversion
nថ ␾ ⫽ ␣关2␳ aa 共 n៮ ␾ ⫹ 1兲 ⫺ 共␳ bb ⫹ ␳ cc ⫹ ␳ bc
⫹ ␳ cb 兲n̄ ␾ 兴 (5)
where the elements of the density matrix are

冉 冊
the analysis of a photo-Carnot QHE driven by a Solving for n̄␾ in steady state we find given by
multi-mode radiation field (18). kT h
The stimulus for our work came from two n៮ ⌽ ⬵ n៮ (1⫺n៮ εcos␾) ⬵
ប⍀
(1 ⫺ n̄εcos␾) (3) ␳ aa 0 0
innovations in quantum optics: the micromaser
␳ bb ␳ bc ⫽

Downloaded from https://www.science.org at Chalmers University of Technology on December 03, 2021

(microlaser) (19) and lasing without inversion where n៮ ⫽ [(Pb ⫹ Pc)/2Pa ⫺ 1]⫺1 is the
0
(3). In micromasers and microlasers, the radia- average photon number in the absence of 0 ␳ cb ␳ cc
tion cavity lifetime is so long that a modest atomic coherence. When ⍀ ⬎⬎ ␻ (Fig. 1C),
beam of excited atoms can sustain laser oscil- n៮ ⫽ (exp(ប⍀/kTh) ⫺ 1)⫺1. Here, k is the
Pa 0 0

lation. In LWI, the atoms have a nearly degen-
erate pair of levels making up the ground state
(Fig. 1C). When the lower level pair is coher-
ently prepared, a small excited state population
can yield lasing (without inversion). Here, the
“engine” is a microlaser cavity in which one
mirror is a piston driven by the radiation pres-
sure (20) given by
PV ⫽ ប⍀ n៮ (1)
where P is the radiation pressure, V is the
Boltzmann constant.
The radiation field generated by phase-
coherent atoms is still a thermal field. That is,
n៮ ␾ and all higher order moments are charac-
terized by a single temperature T␾ (10, 11).
Thus, we write n៮ ␾ ⫽ kT␾/ប⍀, which taken
together with Eq. 3 yields
T␾ ⫽ T h(1⫺n៮ εcos␾) (4)
This is our main result. If we adjust the
relative phase between b and c by, for exam-
ple, varying the phase of a microwave field
冢 冣
0 P b ⫹⌬ ␳ bc
0 ␳ cb P c ⫺⌬
In Eqs. 5 and 6, the off-diagonal element ␳bc
describes, or perhaps better defines, the co-
herence between b and c. This coherence is
model-dependent, and the case of micro-
wave-induced coherence is discussed. The
concomitant changes in Pb and Pc, denoted
by ⌬ in Eq. 6, are negligible.
Comparing Eqs. 5 and 6, we see that ε ⫽
2ⱍ␳bcⱍ/(Pb ⫹ Pc) because ␳bc ⫹ ␳cb ⫽
2ⱍ␳bcⱍcos␾. In the high-temperature limit, Pb
⬃ Pc ⬃ 1/3, which gives ε ⫽ 3ⱍ␳bcⱍ.
The preceding basics provide a foundation
for treating the single-mode “photon” QHE.
Here, we focus on a Carnot cycle operation
consisting of four steps (Fig. 2): (i) isother-
mal expansion from 1 to 2 at a higher tem-
perature determined by the thermally excited
atoms, (ii) shutting off of the atomic beam

Fig. 1. (A) Photo-Carnot engine in which radiation pressure from a thermally excited single-mode field
drives a piston. Atoms flow through the engine and keep the field at a constant temperature Trad for the
isothermal 1 3 2 portion of the Carnot cycle (Fig. 2). Upon exiting the engine, the bath atoms are cooler
than when they entered and are reheated by interactions with the hohlraum at Th and “stored” in
preparation for the next cycle. The combination of reheating and storing is depicted in (A) as the heat
reservoir. A cold reservoir at Tc provides the entropy sink. (B) Two-level atoms in a regular thermal
distribution, determined by temperature Th, heat the driving radiation to Trad ⫽ Th such that the regular
operating efficiency is given by ␩. (C) When the field is heated, however, by a phaseonium in which the
ground state doublet has a small amount of coherence and the populations of levels a, b, and c, are
thermally distributed, the field temperature is Trad ⬎ Th, and the operating efficiency is given by ␩␾,
where ␲ can be read off from Eq. 7. (D) A free electron propagates coherently from holes b and c with
amplitudes B and C to point a on screen. The probability of the electron landing at point a shows the
characteristic pattern of interference between (partially) coherent waves. (E) A bound atomic electron Fig. 2. Temperature-entropy diagram for Car-
is excited by the radiation field from a coherent superposition of levels b and c with amplitudes B and not cycle engine. In the present QHE, Qin is
C to level a. The probability of exciting the electron to level a displays the same kind of interference provided by the hot atoms. When Th ⫽ Tc, the
behavior as in the case of free electrons; i.e., as we change the relative phase between levels b and c, photo-Carnot engine can still produce useful
by, for example, changing the phase of the microwave field which prepares the coherence, the work if the coherent three-level heat bath at-
probability of exciting the atom varies sinusoidally, as indicated in Eq. 4. oms (Fig. 1C) are “phased” such that ␾ ⫽ ␲.

www.sciencemag.org SCIENCE VOL 299 7 FEBRUARY 2003 863

 REPORTS
and subsequent adiabatic expansion from 2 to
3, (iii) establishment of thermal contact with
the entropy sink to effect isothermal com-
pression from 3 to 4 at temperature Tc, and
(iv) breaking of thermal contact and contin-
uance of adiabatic compression from 4 to 1.
We define the efficiency of the photo-
Carnot engine as ␩ ⫽ (Qin ⫺ Qout)/Qin ⫽
(Th S12 ⫹ TcS43)/ThS12. In the high-temper-
ature (kT ⬎⬎ ប⍀) and small expansion
(⌬⍀ ⫽ ⍀1 ⫺ ⍀2 ⬍⬍ ⍀) limits, S12 ⫽ S43 ⫽
k⌬⍀/⍀.
Engine efficiency, when fueled by regular
thermal atoms, is then given by ␩ ⫽ 1 ⫹
(Tc S34/ThS12 ) ⫽ 1 ⫺ Tc/Th. However,
when the radiation working fluid is heated
rent interest (22). In the particular form of
nonequilibrium considered here, quantum co-
herence, the phase ␾ is found to be a demon-
esque control parameter that allows work to
be extracted from a single bath. The total
system entropy is constantly increasing, and
the physics behind the second law is not
violated. However, quantum coherence does
allow certain features of engine operation
beyond the classical limit.
References and Notes
1. For an in-depth treatment, see K. Annamalai and I.
Puri, Advanced Thermodynamic Engineering (CRC
Press, Boca Raton, FL, 2001).
2. M. O. Scully, M. S. Zubairy, Quantum Optics (Cam-
bridge Press, London, 1997).
cy continuously changes during the passage of atoms
through the cavity: the atoms may go out of reso-
nance. To preserve resonance, we needed to contin-
uously change the level spacing of the atoms. This
can be accomplished in several ways, but for the
present purposes we will simply take such atomic
fine tuning as a given. Further discussion will be given
elsewhere.
22. See, for example, the conference proceedings on the
subject referred to in (10, 11) and references therein.
23. O. Kocharovskaya, Phys. Rep. 219, 175 (1992).
24. E. Arimondo, Prog. Opt. 35, 257 (1996).
25. S. Harris, Phys. Today 50, 36 (1997).
26. M. Scully, S.-Y. Zhu, A. Gavrielides, Phys. Rev. Lett. 62,
2813 (1989).
27. H. S. Leff, A. F. Rex, Eds., Maxwell’s Demon (Adam
Hilger, Bristol, 1990).
28. H. C. von Baeyer, Warmth Disperses and Time Passes
(Random House, New York, 1999).
29. C. Bennett, Sci. Am. 257, 108 (1987).

㛬㛬㛬㛬
3. Reviews of LWI are to be found in (23–25). The 30. S. Lloyd, Phys. Rev. A 39, 5378 (1989).
by phase-coherent atoms, Th 3 T␾ and the 31. , Phys. Rev. A 56, 3374 (1997).
present scheme is closest to the lasing without in-
Carnot efficiency is given by version model of (26). 32. T. Freedmann et al., Phys. Rev. E 61, 4774 (2000).
4. For example (27, 28). 33. R. Kosloff, E. Geva, J. Gordon, J. Appl. Phys. 87, 8093
Tc (2000).
␩␾ ⫽ ␩ ⫺ 3n̄ⱍ␳ bc ⱍcos␾ (7) 5. H. Linke et al., Science 286, 2314 (1999).

Downloaded from https://www.science.org at Chalmers University of Technology on December 03, 2021

Th
where ε ⫽ 3ⱍ␳bcⱍ ⬍⬍ 1. Hence, ␩␾ ⬎ ␩ when,
for example, ␾ ⫽ ␲.
We see from Eq. 7 that when Th ⫽ Tc and
␩␾ ⫽ 3n៮ ⱍ␳bcⱍ, the photon engine produces
work from a single heat bath. The net work
produced, when Th ⫽ Tc, is
n៮ ␪ ␮ ប␻ ⌬⍀ ⌬⍀
Wnet ⫽ ␩␾T c S 12 ⬇ kT c ⫽ n៮ ␪ ␮ ប␻
kT ⍀ ⍀
(8)
where the “Rabi flopping” angle ␪␮ is the
(small) tipping angle defined below.
The atomic coherence can be generated,
for example, by passage of the atoms through
a microwave field (12), which may be ap-
proximated by a coherent state ⱍ␣␮典 that has a
mean photon number N␮ ⫽ ⱍ␣␮ⱍ2. If the
resonant atom-field coupling frequency is g␮,
and the interaction time is ␶␮, then ␳bc ⬇ ␪␮
exp(i␾ )ប␻/3kT, where ␪␮ ⫽ g␮␶␮ⱍ␣␮ⱍ and
we have taken the high-temperature limit
␳cc ⫺ ␳bb ⬇ ប␻/3kT. We may then write
3n៮ ⱍ␳bcⱍ ⫽ n៮ ␪␮ប␻/kT. Hence if we take rea-
sonable values; ␪␮ ⬇ 0.1, ␻/⍀ ⬇ 0.1, and n៮
⬇ 103, we find ⱍ␳bcⱍ ⬇ 3 ⫻ 10⫺6. Hence, for
ⱍ␳bcⱍ of order 10⫺5, efficiencies ␩␾ are of a
few percent (10, 11) even though Th ⫽ Tc.
Heating effects governed by ⌬ are unim-
portant in determining the temperature of the
field. The atomic density matrix after micro-
wave preparation is given by Eq. 6, where
⌬ ⬃ ␪␮ 2
ប␻/kT is higher order in ␪␮. Further-
more, the effects of ⌬ cancel out as can be
seen in Eq. 5 and if ␳bb is replaced with Pb ⫹
⌬ and ␳cc is replaced with Pc ⫺ ⌬. Hence, the
physics is contained in ␳bc.
We can estimate the microwave energy,
W␮, necessary to produce coherence between
b and c, given the preceding microscopic
model of our QHE (10, 11). The important
point is that we find W␮ ⬇ 5Wnet, i.e., W␮ ⬎
Wnet in the present QHE.
The quantum thermodynamics of systems
slightly out of equilibrium is an area of cur-
6. Two classic papers on information erasure and relat- 34. S. Haroche, D. Kleppner, Phys. Today 42 (no. 1), 24
ed subjects are (29, 30). (1989).
㛬㛬㛬㛬
7. M. Scully, Phys. Rev. Lett. 87, 220601 (2001). 35. P. R. Berman, Ed., Cavity Quantum Electrodynamics
8. , Phys. Rev. Lett. 88, 050602 (2002). (Academic Press, Boston, 1994), p. 57.
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D. Sheehan, Ed. (AIP Press, New York, 2002), pp. 38. M.O.S. wishes to thank N. Ramsey for many stimu-
92–97. lating and helpful discussions. This paper is an out-
12. Y. Rostovstev, Z. Sariyianni, M. Scully, in preparation. growth of QHE discussions with D. Kleppner, F. Nar-
13. N. Ramsey, Phys. Rev. 103, 20 (1956). ducci, T. Opatrny, and N. Ramsey at the TAMU-ONR
14. H. Skovil, E. Schultz-Dubois, Phys. Rev. Lett. 2, 262 2001 workshop. Useful conversations on the subject
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16. C. Bender, D. Brody, and B. Keister, Proc. R. Soc. edged, as are helpful discussions on the present
London A 458, 1519 (2002). manuscript with K. Annamalai, K. Chapin, R. Curl, D.
17. T. Opatrny, M. Scully, Fortschr. Phys. 50, 657 (2002). Depatie, B.-G. Englert, E. Fry, R. Hulet, C. Joachain, K.
18. M. H. Lee, Am. J. Phys. 69, 874 (2001). Kapale, V. Kocharovsky, S. Lloyd, A. Muthukrishnan, T.
19. D. Meschede, H. Walther, G. Muller, Phys. Rev. Lett. Opatrny, M. Pilloff, Y. Rostovtsev, Z. Sariyianni, and
54, 551 (1985). For discussion of cavity QED, see (34, G. Sussmann. We thank R. Haden, the Texas Engi-
35). For the quantum theory of a micromaser, see neering Experiment Station, the Office of Naval Re-
(36). For the first demonstration of the microlaser, search, the DARPA-QuIST program, and the Welch
see (37). Foundation for supporting this research.
20. M. Kim, F. Narducci, M. O. Scully, M. S. Zubairy, in
Spectroscopy of Systems with Spatially Confined 1 October 2002; accepted 16 December 2002
Structures, B. Di Bartolo, Ed. (Kluwer, Netherlands Published online 2 January 2003;
2002). 10.1126/science.1078955
21. A complication arises as the cavity resonant frequen- Include this information when citing this paper.
Au20: A Tetrahedral Cluster
Jun Li,1 Xi Li,1,2 Hua-Jin Zhai,1,2 Lai-Sheng Wang1,2*
Photoelectron spectroscopy revealed that a 20-atom gold cluster has an ex-
tremely large energy gap, which is even greater than that of C60, and an electron
affinity comparable with that of C60. This observation suggests that the Au20
cluster should be highly stable and chemically inert. Using relativistic density
functional calculations, we found that Au20 possesses a tetrahedral structure,
which is a fragment of the face-centered cubic lattice of bulk gold with a small
structural relaxation. Au20 is thus a unique molecule with atomic packing
similar to that of bulk gold but with very different properties.
Small clusters often have different physical and stability relative to other reagents and to other
chemical properties than their bulk counter- clusters of the same material. A closed electron
parts. Materials assembled from finite-sized configuration with a large energy gap between
clusters have been intensively sought ever since the highest occupied molecular orbital
the discovery of C60 (1). One of the criteria for (HOMO) and the lowest unoccupied molecular
a cluster to be used as a potential building block orbital (LUMO) is a prerequisite for the chem-
for cluster-assembled materials is its chemical ical stability of a cluster. Besides its high sym-

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 Extracting Work from a Single Heat Bath via Vanishing Quantum Coherence
Marlan O. Scully, M. Suhail Zubairy, Girish S. Agarwal, and Herbert Walther

Science, 299 (5608), • DOI: 10.1126/science.1078955

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