Volume 12, number 2 OPTICS COMMUNICATIONS October 1974

THERMODYNAMICS OF ADIABATIC LASER PROCESSES:

OPTICAL HEATERS AND REFRIGERATORS*

O. KAFRI * and R.D. LEVINE*

The Hebrew University, Jerusalem, Israel

Received 6 June 1974

A thermodynamic operating condition for lasing (in the presence of losses) is derived. This provides a lower bound
for the required density of systems in the emitting level. Efficient cooling enables one to reduce this bound. The re-
suits are shown to be a particular application of the thermodynamic limitations on heating or refrigeration achieved
via luminescence.

1. Introduction 2. The entropy cycle

Thermodynamic considerations can readily be ap-
plied to the absorption and emission of light by some
medium [ 1 - 5 ] . Such analysis is particularly useful
when the energies of the absorbed and emitted light
differ. The energy balance is made up by the energy
removed from (or provided by) the active medium.
Thermodynamics centers attention on the need to ex-
amine not just the energy but also the entropy bal-
ance. In this communication we consider adiabatic
processes, where the active medium is not (necessarily)
coupled to a heat bath. In particular we consider laser-
induced Stokes and anti-Stokes transitions and laser
emission in adiabatic processes.
Section 2 considers the entropy balance in an opti-
cal excitation/deexcitation process with special atten-
tion to the entropic consequences of the need to dissi-
pate (or generate) energy in the medium. As an exam-
ple, a finite gain laser with a finite specific heat is con-
sidered in section 3. Optical heating and refrigeration
are considered in section 4.
In order to consider the thermodynamic balance in
optical processes it is convenient to consider three
stages. In the first (the 'pumping') stage the energy
(and consequently the entropy) of the active medium
is increased by the excitation process. In the second
(the 'dissipation') stage the populations of the differ-
ent energy levels of the medium (and hence the en-
tropy* 1) change due to internal relaxation processes.
When the medium is coupled to a heat bath, this stage
corresponds to flow of heat out of (or into) the medi-
um. Otherwise this stage corresponds to a redistribu-
tion of the energy pumped-in in the first stage. As a
simple example consider a three-level system where
the pumping corresponds to an optical transition
from level 1 to level 3 (fig. 1). ASp, the change in en-
tropy in the pumping stage is a measure of the changes
in the populations of levels 1 and 3 which occur due
to the excitation process. As a result of the distur-
bance caused by the pumping the medium relaxes (iso-
thermally or otherwise) towards a new distribution of
the populations. The accompanied change in the en-
tropy is AS M . For an isothermal process AS M = Q / T

* Acknowledgement is made to the donors of the Petroleum
Research Fund, administered by the American Chemical
Society for their support of this research
School of Applied Science and Technology.
* Department of Physical Chemistry.
~1 We are using here the information-theoretical definition
of the entropy [6, 7] which is a measure of the distribu-
tion of the population over the different accessible quan-
tum states. This definition reduces to the well known re-
suits when equilibrium is maintained.

118
Volume 12, number 2 OPTICS COMMUNICATIONS
2 l ~'SM
>- ~- k o ,,s.
Z 2
AS M ~ASp - aS~ : .~Sp + AS L
Fig. 1. Energy and entropy balance in a heating process. The
energy Ep - E ~ is dissipated by the medium. (a) Ordinary (in-
coherent) fluorescence. The entropy generated in the pump-
hag stage (i-+j) is larger than the entropy dissipated by the
medium ( / ~ k). The emission stage (k ~ i) yields light at a
positive temperature. (b) Laser emission. Here, due to a larger
magnitude of ASM (achieved, say, by cooling the medium)
the entropy increases during the luminescence, reflecting a pos-
itive gain transition. (Note that ~S L = - ~ S ~ , by definition).
where Q is the amount o f heat removed at the temper-
ature T. Otherwise A S M can be computed from the re-
suiting changes in the populations, and has invariably
the interpretation as (positive) increase in the entropy
due to the relaxation of the medium.
In the final stage the medium lowers its energy b y
light emission. The resulting change in the entropy o f
the medium is AS L. For ordinary emission the 'cool-
ing' o f the medium implies that A S L < 0, i.e.
A S L = - A S p . Here ASp is the (positive) e n t r o p y
change resulting from reversing the emission stage (fig.
1). For emission from an inverted population (where
amplification is possible) [5], A S L ~> 0 corresponding
to the result [8] that a cooling o f ' i n v e r t e d ' population
is accompanied by an increase in the entropy.
Since the total change in the entropy o f the medi-
um must be non-negative we obtain that
A S M /> ASp + AS L
or, for ordinary emission by the medium
A S M 1> ASp -- A S ; .
In these expressions ASp is governed by the details o f
the pumping process and A S M by the relaxation routes
open to the medium. Both terms are thus subject to
some experimental control. The significance o f the
equation is that it provides an upper b o u n d on A S L.
Thus if lasing is to take place one must have in prac-
tice .2 that A S L > 0.
,2 The equality sign is ruled out by the need to maintain a non-
zero gain, see section 3 below.
October 1974
f
Ep
s~
A SM >tA Sp-A SIp
Fig. 2. Energy and entropy balance in an anti-Stokes process.
Here, since energy is provided by the medium ASp < AS~
(eq. (13)) so that the emitted light carries more entropy than
the exciting light and no inversion is possible.
Fig. 1 illustrates the above consideration for a three
level system. Pumping connects levels 1 and 3, the re-
laxation process connects levels 3 and 2. Eight emis-
sion is from level 2 to 1. Two entropy cycles are indi-
cated. (a) Ordinary emission, where A S L < 0, i.e. the
light emitted at a positive temperature Tp ( A S L =
-EL/Tp) and (b) laser emission. Similar considera-
tions would apply when the emission is from level 3
to level 2 and the dissipation is from level 2 to level 1
(e.g. as in some metal ion lasers). Fig. 2 illustrates an
anti-Stokes process in a three level system. A cycle for
laser emission is not shown and, as will be clearer later,
thermodynamic considerations indeed show that laser
emission is impossible in an anti-Stokes process.
Similar considerations apply for luminescence pro-
cesses where the initial excitation need not be optical
but could be pure work [3] or electrical [9] or chem-
ical [10].
(1)
3. The adiabatic laser
The thermodynamic threshold condition for lasing
(2)
is A S L = 0. In practice, in order to overcome inherent
losses the laser must operate at a finite gain [11]. For
any given transition, say 2 -+ 1, there must be a thres-
hold value for t h e excess density in level 2, N 2 - N 1
> / A N t h , if oscillations are to be maintained. A given
excess density may obviously be achieved with dif-
ferent values o f N 2 (and of N1). Since the pump-
ing process serves to promote systems to level 2,
it is obviously desirable to operate at the lowest value
o f N 2 consistent with a given value of A N = N 2 - N 1 .
119
Volume 12, number 2
As one can show [5] that (k is Boltzmann's constant)
A S L = k In (N2/N 1),
it follows that
N2/(N 2 Sl) = 1/[1- exp(--ASL/k)].
For a given finite gain (where gain coN2 N 1 ) the op-
timal operating conditions correspond therefore to a
maximal value of AS L. The largest possible value of
AS L under given operating conditions is determined
by the thermodynamic considerations, eq. (1), as
AS L < AS M -- ASp.
Eq. (5) provides an upper (thermodynamic) limit
on AS L and hence, through eq. (4), a lower bound
for N2, the density of system in the upper level, for a
given gain. In particular at the threshold value of the
excess population [11 ], eq. (4) predicts the threshold
value o f N 2. Both ASp and AS M are subject to experi-
mental control, and to minimize N 2 one needs to
maximize AS M or minimize ASp, or both.
Consider the pumping process as coupling the sys-
tem (through a filter for the energy Ep) to a heat bath
at a temperature rp [41. Then ASp = Ep/Tp and one
needs to operate at the highest possible Tp, or, in gen-
eral the pumping process needs to be as near to 'pure'
work (in the thermodynamic sense) as possible. For
optical pumping the temperature of the light source
should be as high as possible .3 .
For an adiabatic laser any excess energy not re-
moved as laser emission (i.e. Ep - EL) is dissipated as
heat in the medium. If C is the specific heat and T the
initial temperature of the medium then the final tem-
perature T' is given by
Ep - E L = C ( T ' - T),
so that
A S M = Cln ( T ' / T ) = Cln [l + ( E p - E L ) / T C ] .
Using the inequality In (1 + x) ~<x it follows that
AS M < (Ep - EL)/T,
with equality only when (Ep - EL)IT ~ C.
.3 Ideally, a laser at the frequency Ep/h. Since the laser light
is well collimated and very nearly monochromatic it brings
in practically no entropy [1,2].
120
OPTICS COMMUNICATIONS October 1974
The largest possible value of AS M is thus obtained
in the isothermal limit, C-+ ~ (so that T'-+ T) and
(3)
particularly so when T-+ 0. The specific heat C of the
medium is increased, in practice, by insuring that the
optical levels are efficiently coupled to a large, inert
(4)
buffer medium, which serves as the heat bath. If the
rate of energy transfer from the optical medium to
the buffer medium is slow, the 'effective' C decreases
and so does AS M. Thus, for inefficient dissipation,
more systems need be pumped into level 2 to main-
tain the same gain. While similar conclusions can be
obtained by considering rate (or kinetic) equations,
(5)
the present approach offers a credible alternative.
The efficiency of the laser is given by .4
r? = 1 - C ( T ' - T)/Ep (9)
and since
T' = T exp (ASM/C), (10)
we have that
r~ = 1 -- (CT/Ep)[exp (ASM/C) --1], (1 1)
with the largest efficiency obtained at the thermody-
namic threshold (zero gain) limit when AS M = ASp.
At a finite gain AS M > ASp (where ASp is constant
for a given pumping process) and hence the efficiency
at a finite gain is always below the efficiency at thres-
hold.
For a given pumping process and AS L, the maxi-
mal efficiency is obtained for isothermal operation.
This readily follows from the inequality exp (x) ~<
1 + x which implies that
r~ <~ 1 - T A S M / E p (12)
with equality in the limit C-+
(6)
4. Optical heating and refrigeration
(7)
Luminescence in which the energy of the pumping
process differs from that of the emitted light can be
(8) regarded, on the basis of the first law, as a heating or
~4 In general the thermodynamic efficiency is given by
=1 ~. Oil ~. qj"
z 1
Here qj denotes heat absorbed at the stage j and Qi de-
notes heat given out at the stage i.
Volume 12, n u m b e r 2 OPTICS COMMUNICATIONS
a refrigeration process. It is interesting to note that a
similar conclusion follows from the second law. Thus,
if Ep and Tp are the energy and temperature of the
luminescence it follows from (2) and (7) that
Et t
Ep P <~ Cln [I+(Ep-Ep)/TC]. (13)
Thus for a heating process, where Q = Ep - E p > 0,
AS M > 0. In fact, we saw in section 3 that for a
Stokes (Q > 0) process AS L = AS M - Ep/Tp can
be positive, leading to laser action. Eq. (13) then
r
provides a bound for the 'hottest' possible T L =-Tp,
(AS L = --EL/TL).
For an anti-Stokes process, where some of the lu-
minescence energy is provided by the medium
(Q <(0), AS M "~ 0. In an anti-Stokes process, the en-
tropy of the medium goes down. While the conclusion
is rather obvious (the medium, after all, cools down)
it does necessarily imply, using (13) that T'p < Tp and
since Tp is positive (or at most tends to +oo) one can-
not, on the basis of the second law of thermodynamics,
create a population inversion using an anti-Stokeg"
transition. After all, if one could, the device would
convert some heat from the medium to pure work.
(Indeed, a proof can be given directly in terms of this
restriction). Thus, even for a laser-induced anti-Stokes
process [12] the luminescence is incoherent* s.
One can, of course, achieve an inverted population
between two levels, at an energy E L apart, even if
E L > Ep. This could be achieved in a chemical laser
(a case analogous to that of an electrochemical cell)
and other pumping processes which differ from optical
excitation in that ASp can be negative .6 . Another pos-
sible way of achieving laser emission in a nominally
anti-Strikes process is when other processes are coupled
to the medium so that the overall AS M is positive.
The temperature rise (or fall) is determined by eq.
(10) and the efficiency by eq. (9). As expected, the ef-
ficiency for refrigeration can exceed unity, where the
fraction C(T- T')/Ep of Ep is provided by the thermal
, s Strictly speaking, since the laser emission does have a finite
width (in frequency) and a finite angular spread, its light
t e m p e r a t u r e a l t h o u g h very high, is n o t infinite. It is thus
possible, in principle, to obtain nearly m o n o c h r o m a t i c ra-
diation in a purely anti-Stokes emission, b u t with a negligi-
ble efficiency.
, 6 This is not possible for p h o t o n s for which the chemical po-
tential is zero.
October 1974
energy of the medium. In the isothermal limit we ob-
tain
r~ = ( 1 - T/Tp)/(1- TITS). (14)
In the limit Tp ~ co (the conversion of work into in-
coherent light at a temperature Tp) this reduces to the
result of Weinstein [3] which is also correct for laser-
induced excitation processes. In the limit Tp ~ oo
(the thermodynamic threshold for lasing at zero gain)
one obtains the expected Carnot efficiency.
Optical refrigeration can also be applied selectively.
An example is shown in fig. 2. In the absence of opti-
cal excitations assume that level 2 and 1 are coupled
to a heat bath at a temperature T so that
(N2/N1) c~ exp [ - ( E ; - Ep)/k T ] . (15)
When level 2 is pumped-up to level 3 which then de-
cays radiatively to level 1 we have that
N2/N 1 = exp ( ASM/k ). (16)
Using eq. (13) and the fact that for refrigeration T'p
< Tp it is clear that the population ratio has changed
in favour of level 1. As expected, the refrigeration
process has depleted the population of level 2. This
refrigeration process has a potential practical applica-
tion in that it can pump systems out of the final
(lower) level of a laser transition. Such a depletion
would necessarily improve the gain of the transition.
In particular a laser in the infrared could be used to
cool down the lower level for a transition in the visible,
which may then achieve positive gain.
5. Concluding remarks
Thermodynamic considerations are shown to pro-
vide practical limitations on the design parameters of
lasers and, in general, of optical heaters and refrigera-
tors. A particularly important quantity is the amount
of entropy dissipated in the medium AS M . It is the
sign of this entropy that rules out lasing (with finite
gain) in an anti-Stokes process. When AS M is positive,
increasing its magnitude serves to decrease the mini-
mal density of systems (in the 'inverted' level) which
is required for lasing.
121
Volume 12, number 2 OPTICS COMMUNICATION
References
[1] M. Planck, The theory of heat radiation, (Blakiston,
N.Y. 1914).
[2] L. Landau, J. Phys. USSR 10 (1946) 503.
[3] M.A. Weinstein, J. Opt. Soc. Am. 50 (1960) 597.
[4] J.E. Geusic, E.O. Schulz-DuBois and H.E.D. Scovil,
Phys. Rev. 156 (1967) 343.
[5] R.D. Levine and O. Kafri, to be published.
[6] E.T. Jaynes, Phys. Rev. 106 (1957) 620.
122
October 1974
[ 7 ] A. Katz, Principles of Statistical Mechanisc (Freeman,
San Francisco, 1967).
[8] N.F. Ramsey, Phys. Rev. 103 (1956) 20.
[9] G.C. Dousmanis, C.W. Mueller, H. Nelson and
K.G. Petzinger, Phys. Rev. 133 (1964) A316.
[10] R.D. Levine and O. Kafri, Chem. Phys. Letters 27
(1974) 175.
[11 ] A.L. Schawlow and C.1f. Townes, Phys. Rev. 112 (1958)
A1940.
[12] T. Kushida and J.E. Geusic, Phys. Rev. Letters 21
(1968) 1172.