The meaning of "adiabatic"

KEITHJ. LAIDLER
Department of Cllemistr)! University of Ottawa, Ottawct, ON K I N 6N5, Carzcldn
Received May 20, 1993
This paper is dedicated to Professor John C. Polanyi or1 the occasiorl ofhis 65th birtlldcry

KEITHJ. LAIDLERCan. J. Chem. 72, 936 (1 994).

In chemical kinetics the word "adiabatic" has come to refer to a process in which there is no change of quantum state, a mean-
ing that has no connection with the thermodynamic meaning or with the etymology of the word. This usage is traced to early dis-
cussions of reversible adiabatic processes in classical and quantum mechanics, processes that came to be referred to simply as
adiabatic.
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 220.158.190.1 on 11/19/18

KEITHJ. LAIDLERCan. J. Chem. 72,936 (1994).

En cinktique chimique, le mot adiabatiques se refkre aujourd'hui a un processus dans lequel il n'y a pas de changement d'ktat
quantique, une signification qui n'a aucune relation avec le sens thermodynamique ou avec l'itymologie du mot. On peut
retracer I'origine de ce nouvel usage dans les premieres discussions des processus adiabatiques re'versibles de la micanique clas-
sique ou quantique auxquels on a fini parse rifkrer simplement adiabatiques.
[Traduitpar la ridaction]
Introduction entitled "On the mechanical meaning of the second law of ther-
In chemical kinetics the word "adiabatic" has long been used modynamics" (1). In it he claimed to have given a "purely ana-
to refer to a chemical reaction in which the products remain in lytical, completely general, proof of the second law of
the same quantum state as the reactants. This usage has created thermodynamics." By 1868 he had realized that his arguments
some puzzlement as it does not seem to have, and indeed does were ill-conceived, and in that year he published a paper of
not in fact have, any connection with the etymology of the word great importance ( 3 , which initiated his pioneering contribu-
adiabatic, or with the appropriate use of the word in thermody- tions to statistical mechanics. This contribution owed much to
For personal use only.

namics. The word adiabatic means "not passing through," and
in thermodynamics refers to a condition imposed on a system, a
condition that prevents any passage of heat into or out of the
system. In its kinetic usage the word relates not to a condition
imposed on the system, but rather to an inherent property of a
chemical process, namely its tendency under certain conditions
to occur without any change in quantum states.
A consideration of how the kinetic meaning of adiabatic
developed is of some interest in the history of science, and is
also instructive in leading to a better understanding of some of
the fundamental principles of statistical mechanics and quan-
tum mechanics. The trail begins with a paper (1) published in
1866 by Ludwig Boltzmann, in which he mistakenly claimed to
have derived the second law of thermodynamics on the basis of
classical mechanics. Within a few years, thanks to his study of
Clerk Maxwell's papers, he had realized that his argument was
invalid, and that the second law must be explained along statis-
tical lines. In his 1868 paper, however, he had considered a
reversible adiabatic process, and it is from that argument that
the winding and sometimes indistinguishable trail eventually
led, through several false turns, to the inappropriate use of the
word adiabatic in modern kinetics.
"Adiabatic" as used in thermodynamics
The word adiabatic was first used in 1858 by W.J.M. Rankine
(2), and it derives from the Greek prefix a - (a-), not, 8 ~ (dia),
a on the other hand, the ring is lowered rapidly just at the moment
through, and P a ~ v (bainen),
~v to pass. Although it was Rankine
who first used the word, the concept of an adiabatic process, in
which no heat enters or leaves the system, is stated clearly in
Carnot's famous memoir (3) of 1824, and in Clapeyron's math-
ematical treatment of Carnot's cycle (4), which involves two
isothermal and two adiabatic steps.
an important paper by Clerk Maxwell (6) on the distribution of
speeds in gases. Others, however, notably Rudolf Clausius (7,
8) and Coloman (or KAlmAn) Szily von Nagy-Szigeth (9-1 l),
continued to maintain the view that the second law can be
proved on the basis of mechanics.
Although Boltzmann's 1866 paper was invalid, it did involve
a principle that was later helpful in leading to an understanding
of the quantum theory. Boltzmann considered a somewhat arti-
ficial model for a gas in which the molecules undergo a periodic
motion of frequency v. He then proved that if the gas were sub-
jected to a reversible udiubatic change the ratio of the energy E
to the frequency v would remain constant. In their later
Clausius and Szily also considered reversible adiabatic
changes, agreeing with Boltzmann's conclusion that Elv
remains constant. It was at about that time that the word action
began to be applied to the quantity Elv.
Subsequently a number of other workers stressed this invari-
ance of Elv. In 1902, for example, Lord Rayleigh, in a treatment
(12) of the pressure of radiation, considered a simple pendulum
consisting of a bob and a string. By means of a small ring round
the string its length could be altered, and as the string becomes
shorter the frequency of the pendulum increases. Rayleigh
proved that if the ring is lowered extremely slowly (i.e., the pro-
cess is carried out reversibly) work is done on the system and
the energy of the pendulum increases in exact proportion to the
frequency; in other words the action, Elv, remains constant. If,
that the string is vertical, no work is done; the frequency
increases but the energy remains constant, so that the action is
no longer unchanged. Other treatments of the same principle in
relation to other situations were given by Andrade (l3), Morton
(14), and Bhatnagar and Kothari (15).

"Adiabaticity" in classical mechanics "Adiabatic invariance" in quantum theory

Boltzmann was 22 years old in 1866 when he wrote his paper Paul Ehrenfest was particularly effective in his writings on
 the fundamentals of mechanics (16-19), and he laid special
emphasis on this constancy of Elv, in both classical and quan-
tum mechanics. In one paper (16a), published in 191 1, he
extended the principle of invariance of Elv in classical systems,
for processes that are extremely slow, to apply to motions other
than harmonic motions, to which the principle had previously
been restricted. He also extended the argument to quantized sys-
tems, showing that when the parameters of a system in a partic-
ular quantum state are changed slowly, the system remains in
the same quantum state. In this same paper he proved rigorously
that, since Elv is the only property that remains constant if one
brings about a very slow change in the system, this is the only
property that can be quantized. It should be remarked that
although as a matter of convenience we speak of the quantiza-
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tion of energy - and this terminology has been sanctioned by

Einstein and Planck among many others - it is, strictly speak-
ing, the action (Elv) that is quantized. Planck in fact referred to
his constant h (= Elv) as the elementary qitantum of action.
Ehrenfest's analysis in this 191 1 paper (16) threw light on a
difficulty that was troubling many of the leading physicists of
the time. The laws of classical mechanics had been well worked
out to deal with energy transfers that occur when molecules col-
lide. What, however, would be the situation if energies are
quantized? This matter was brought up at the First Solvay Con-
gress, held in Brussels at the end of October, 191 1, only a cou- INITIAL FINAL
ple of weeks after Ehrenfest's paper appeared. H.A. Lorenz, STATE STATE
then professor at Leiden and in the following year to be suc-
For personal use only.

ceeded there by Ehrenfest himself, posed a simple question of

fundamental importance. He imagined a pendulum oscillating
in a particular quantum state, and asked what would happen to
the quantized state if the string were shortened. Ehrenfest had
not been invited to attend the Congress but, according to the
report of the Congress, Einstein immediately and unhesitatingly
answered that if the length were changed infinitely slorvly, the
energy would remain equal to hv. It is known that Einstein had
by that time read Ehrenfest's paper (16a),' and he was probably
also familiar with Rayleigh's treatment of the classical problem.
Although the emphasis had always been on the slowness of
the processes, it was shortly after this meeting that the con-
stancy of Elv began to be referred to as "adiabatic invariance."
This expression was apparently first used in print by Einstein in
a paper (20) that appeared in 1914. This usage by Einstein is
acknowledged in papers by Ehrenfest (19) which appeared in
1916. The English version of these papers, which appeared in
the Philosophical Magazine, was entitled "Adiabatic invariants
and the theory of quanta," and on page 502 appears the follow-
ing significant passage:
"By changing the parameters ... in an infinitely slow way, a
given motion P(a) may be transformed into another
motion P(a'). This special type of influencing upon the
system may be called "a reversible adiabatic affection",
the motion P(a) and P(a') being adiabatically related to
each other [his italics]"
Much the same is said in the Dutch versions of the paper. The
key word "reversible" disappeared in the second part of this
sentence, and was also omitted in latter discussions of the prob-
lem. In some of these later treatments one meets anomalous
phrases like "...if a process occurs adiabatically, i.e., very
' ~ e f e r e n c e16a appeared in October, 191 1, and the fact that Einstein
had read it before the Solvay Congress, which occurred at the end of
October, is known from the fact that he referred to it in a letter to his
friend M. Besso dated 21st October, 191 L.
ANGLE OF TWIST
FIG. 1. Schematic potential-energy diagram for the cis-trnrls
isomerization of a substituted ethylene.
slowly...". The emphasis should, of course, be on the re-
versibility and not on the adiabaticity; the same effect would be
obtained if the process were reversible and isothermal. The
important point, as stressed by Einstein at the Solvay Congress,
is that processes must be slow in order for quantum states to be
preserved. In spite of this, the inappropriate word adiabatic
came to be used.
"Adiabaticity" in chemical kinetics
The modern use of the word adiabatic in chemical kinetics is
consistent with the usage introduced by Einstein and Ehrenfest.
The first use in kinetics appears to have been by Fritz London
(21) in 1928, in connection with his approximate quantum-
mechanical expression for the energy of the H...H...H complex,
an intermediate in the H + Hz reaction. In discussing this prob-
lem London suggested that many chemical reactions proceed
"adiabatically," by which he meant that there is no abrupt jump
from one quantum state to another.
Reactions that are not adiabatic in this sense are referred to as
diabatic or nonadiabatic. Examples of nonadiabatic reactions
are the cis-trans isomerizations of certain substituted ethylenes.
Figure 1 shows a schematic potential-energy profile (22) for
such a system, the energy being plotted against the angle of
twist about the double bond. There is a triplet excited state hav-
ing a minimum corresponding to a twist of 90°so that there are
two alternative reaction paths. The system may remain in a sin-
glet state throughout and proceed via point A, where there is a
crossing of two singlet states; this process is referred to as adi-
 938 CAN. J. CHEM. VOL. 72, 1991
abatic. Alternatively, the system may cross to the triplet state at
B and cross to the singlet state at C; this is the non-adiabatic pro-
cess. T h e adiabatic process has a higher activation energy than
the non-adiabatic process, but has a normal pre-exponential fac-
tor, since there is little restriction to passing from a singlet state
to another singlet state. The non-adiabatic process has a lower
activation energy but a lower pre-exponential factor because of
the difficulty in crossing from a singlet to a triplet state. The
evidence for the cis-trans isomerizations is that the pre-
exponential factors are abnormally low by a factor of about
this factor, referred to as the transmissioiz coeflcient for
the reaction, reflects the low probability of transition between
singlet and triplet states.
Systems approaching B in Fig. 1 d o so at various speeds.
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According to the principles enunciated by Ehrenfest and Ein-
stein, systems moving very slowly will inevitably remain in the
triplet state, but these will have insufficient energy to reach C
and will therefore not undergo isomerization. Systems moving
more rapidly will have a significant possibility of jumping into
the triplet state where they will probably undergo a number of
vibrations before passing into the product state. The details are
obviously a matter of great complexity.
The word adiabatic has also been used in kinetics in a more
specialized sense: a reaction in which the system remains in the
same vibrational state has been said to be "vibrationally adia-
batic." In conventional transition-state theory (23, 24) the initial
and activated states are treated quantum mechanically, but the
For personal use only.
passage over the col is treated classically. Also, in the earlier
dynamical treatments of the motion of systems over potential-
energy surfaces, the initial states are quantized but the actual
motion follows classical laws (25), so that the products d o not
appear in their appropriate quantum states. Some attempts have
been made to develop extensions of conventional transi-
tion-state theory in which the motions are constrained to remain
in quantum states (26, 27), and these have been referred to as
adiabatic transition-state treatments. In a number of publica-
tions Polanyi and co-workers have dealt with the theory (28) of
this type of adiabaticity and have provided examples (29). Other
treatments consistent with this type of adiabaticity have been
put forward by Garrett and Truhlar (30), and by Quack and Troe
(31, 32) who have proposed an "adiabatic channel model,"
which is a detailed version of adiabatic transition-state theory.
The word adiabatic in its kinetic sense also appears in Mar-
cus's theory of unimolecular gas reactions (33, 34), often
referred to as Rice-Ramsperger-Kassel-Marcus (RRKM)
theory. Certain types of energy residing in a molecule are
regarded as inactive o r adiabatic; what is meant is that energy of
this type remains in the same quantum state during reaction and
therefore makes no contribution to the rearrangement of bonds
that occurs during reaction. The zero-point energy is adiabatic
in this sense, as is the energy of overall translation and rotation,
since this energy is preserved when the energized molecule
becomes an activated complex. Other energies, such as some
vibrational energies, are said in RRKM theory to be active or
non-adiabatic.
Discussion
It is evident that besides being used in kinetics in a sense that
is different from the thermodynamic sense, the words adiabatic,
diabatic, and non-adiabatic are used in different ways by differ-
ent writers on kinetics. It is obviously of the greatest importance
that whenever the words are used in kinetics they should b e
clearly defined. It should also be noted that the words are often
used not to describe the way in which a reaction is believed to
proceed, but rather the approximation that is being used in the
theoretical treatment of the reaction.
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