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Perspective – life and death of a photon: an intuitive

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Cite this: DOI: 10.1039/d0pp00274g

non-equilibrium thermodynamic distinction
between photochemistry and thermochemistry
Brian Chapman *a and Denis Loiselleb

Received 14th August 2020,
Accepted 3rd November 2020
DOI: 10.1039/d0pp00274g
rsc.li/pps
Neither the thermodynamically determined probability isotherm nor its kinetically manifest rate isotherm
can be applied to photo-absorptive reactions such that the participants, including photons, may be
treated as if they were chemical reactants. Photons and chemical reactants differ from each other funda-
mentally: firstly, a photon’s energy is absolute and, in all instances of practical relevance to the present
paper, independent of its surrounding electrochemical field, while the energy of a chemical reactant is
relative and defined by its surrounding field; secondly, while both photons and chemical reactants can
and do engage in entropy creation, only chemical reactants can engage in entropy exchange. Clarification
of these differences requires identification and abandonment of fundamental historical errors in photo-
chemical thought deriving from inappropriate overreach of analogies drawn between light and ideal
gases, and including: treatment of photo-absorption as a reversible chemical reaction; attribution to light
of thermal potential, or temperature (as distinct from the idealised abstraction of a ‘temperature signa-
ture’); attribution to light of exchangeable entropy content. We begin by addressing widespread misappre-
hensions concerning the perennially misunderstood concept of entropy and the frequently overlooked
distinction between entropy creation and entropy exchange. Armed with these clarifications, we arrive at
a useful perspective for understanding energy absorption and transfer in photosynthetic processes which,
through the chemical ‘kidnapping’ of metastable excited states within structured metabolic pathways,
achieves outcomes which the Second Law denies to thermal chemical reactions.

Introduction – how should we think
about entropy?
In this perspective we shall be challenging what we believe to
be three historical misconceptions in photochemical thought
pertaining to (i) the reversibility of photoabsorption, (ii) the
attribution of temperature to light and (iii) the attribution of
exchangeable entropy content to light. Dealing with the third
of these misconceptions requires us to commence by addres-
sing some crucial areas of misunderstanding in mainstream
thermochemistry concerning entropy so as to clarify the posi-
tion for photochemistry; this will involve development of what
we hope will be a helpful and instructive distinction between
changes in free energy and bound energy in chemical reactions,
based on the fundamental distinction between entropy creation
and entropy exchange, respectively.
Entropy has always been an arcane concept that few fully
understand with unalloyed confidence. In particular, the
a
Honorary Principal Research Fellow, School of Health and Life Sciences, Federation
University Australia, Victoria, Australia. E-mail: brian.chapman@federation.edu.au
b
Honorary Member, Department of Physiology and the Auckland Bioengineering
Institute, The University of Auckland, Auckland, New Zealand
crucial distinction between entropy creation and entropy
exchange is unfamiliar to many scientists, as will become appar-
ent when we consider the incorrect but not uncommon prop-
osition that a useful distinction can be drawn between entropy-
driven chemical reactions and those that are enthalpy-driven.
Despite these uncertainties, or perhaps because of them, some
investigators are occasionally moved to issue purportedly
weighty statements about entropy and Life on Earth, typified by
the following two passages – the first published by Katchalsky
in 19651 and the second published by Endres in 2017:2
1. Several years ago, Prigogine pointed out that steady
nonequilibrium systems produce entropy at a minimal rate. This
remarkable conclusion from Onsager’s law sheds new light on
“the wisdom of living organisms”. Life is a constant struggle
against the tendency to produce entropy by irreversible pro-
cesses. The synthesis of large and information-rich macro-
molecules, the formation of intricately structured cells, the
development of organization – all these are powerful anti-
entropic forces. But since there is no possibility of escaping
the entropic doom imposed upon all natural phenomena
under the Second Law of thermodynamics, living organisms
choose the least evil – they produce entropy at a minimal rate
by maintaining a steady state (Katchalsky, pp. 200–201).

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2. For the last 150 years, there has been speculation that
universal extremal principles determine what happens in
nature,† most prominent being the maximum entropy pro-
duction principle (MaxEPP)*. Its most important conclusion is
that there is life on Earth, or the biosphere as a whole,
because ordered living structures help dissipate the energy
from the sun on our planet more quickly as heat than just
absorption of light by rocks and water* (Endres, p.1).
Clearly, at least one of the above mutually contradictory per-
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Intuitive non-equilibrium
thermodynamics of thermochemical
reactions
We begin with an exposition adapted from an Appendix,
requested from us as part of the peer review process of our
earlier paper,4 dealing with the distinction between entropy
exchange and entropy creation in a transition between states A

spectives must be quite seriously wrong; modern cellular and and B specified as
molecular biology reveals the first perspective to be at least kf

*
A)
B ð1Þ
naïve‡ while a moment’s reflection on global photosynthesis kb
and its relation to the global meat industry exposes the second
perspective as nonsense. where the ratio of the forward and backward rate coefficients,
In pursuing our goal in this perspective we shall use an kf and kb respectively, is determined thermodynamically by the
approach best described as Intuitive Non-Equilibrium equilibrium constant, KAB, thus:
Thermodynamics (INET), which should not be confused with kf
the approach known as Linear Non-Equilibrium ¼ KAB ð2Þ
kb
Thermodynamics (LNET). Our reasons for excluding the latter
approach from useful input into any form of chemistry have The First Law of thermodynamics states that, for such a
been illustrated and discussed elsewhere.§3 state transition, the change in enthalpy (ΔHAB) within the
system relative to its surroundings is equal to the sum of
• the heat (Q) gained by the system from its surroundings,
and
† Three citations have been removed here and a further four and three citations, • any work (W) performed by the surroundings on the
respectively, have been removed at the positions indicated with asterisks in this system, thus:
paragraph.
‡ Even the quasi-stationary states of higher organisms – implicit in the concept ΔH AB ¼ Q þ W ð3Þ
of homeostatic regulation of the relative constancy of their ‘internal environ-
ments’ – are dependent at the very least on the far-from-steady-state cardio- For exothermic transitions that release heat into the sur-
vascular and respiratory cycles, while even the deeply sleeping human brain is roundings, the quantities in eqn (3) are commonly negative
characterised by large electrical oscillations arising from synchronised cyclic
with respect to the system, in which case the situation is
variations in neuronal activity.
§ Interested readers may peruse contrarian views of LNET expressed in this publi-
described by saying that the loss in enthalpy from the system
cation’s “Review History” in response to Reviewer 2 (Appendix A, p.13 and to its surroundings is equal to the sum of
Appendix B, pp. 17–18) which is openly accessible online. • the heat lost by the system to its surroundings, and
• any work performed by the system on the surroundings.
The Second Law of thermodynamics states that, for state
Brian Chapman is a retired transition (1), the change in enthalpy (ΔHAB) within the system
physiologist and educational relative to its surroundings is equal to the sum of
software developer, and remains • the change in Gibbs free energy (GAB) within the system
an active professional concert relative to its surroundings, and
pianist. He has held academic • the product of the temperature (T ) and the entropy
appointments at Monash (SABX) gained by the system from its surroundings by the
University’s Faculty of Medicine process of entropy exchange, thus:
(tenured 1973–89), QED
ΔH AB ¼ ΔGAB þ TΔSAB X ð4Þ
Research Unit (contracted
Director 1994–97) and For spontaneous processes (i.e., those in which ΔGAB < 0),
Gippsland Medical School (con- the quantities on the right side of eqn (4) are commonly
tracted 2008–14), and at Duke different in sign and the situation is thus commonly described
Brian Chapman University Medical Center by saying that the loss in enthalpy from the system to its sur-
(Visiting Associate Professor of roundings is equal to the difference between
Physiology on eight occasions over the period 1975–86). His • the free energy lost by the system to its surroundings, and
research career began with experimental studies of energetics in • the product of the temperature and the entropy gained
skeletal and cardiac muscle in the late 1960s, progressing from by the system from its surroundings.
the mid-1970s toward theoretical studies of consistency between It is also useful to conceive ΔGAB as being the component
thermodynamics and kinetics in bioenergetics where his interests of ΔHAB that is free to do work (hence the term, free energy),
continue to the present. while conceiving the product TΔSABX as being the component

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of ΔHAB that is not free to do work, being inescapably bound
to the material transformation A → B and thus conveniently
and instructively described as bound energy.¶ This conceptual
description will become helpful when we consider the inter-
action of light with matter.
Equating the First Law and Second Law statements, we
have:
ΔGAB þ TΔSAB X ¼ Q þ W ð5Þ
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The Second Law determines that the external work per-
formed by the system on its surroundings can never be greater
in magnitude than the free energy available from the trans-
formation. Thus, for spontaneous processes,
jΔGAB j  jW j ð6Þ
The theoretical limit whereby the work performed is equal
in magnitude to the free energy available is known as thermo-
dynamic equilibrium; at this condition no transformation
takes place, i.e., no work is done and nothing happens. In
order for any transformation to occur, a non-zero amount of
free energy must be dissipated as heat. The thermodynamic
efficiency (η) of transformation is the work (W) performed,
expressed as a fraction of the free energy available, thus:
η ¼ W =ΔGAB  1 ð7Þ
For all non-equilibrium situations, the free energy is either
conserved as work or dissipated as heat in the process of
entropy creation, ΔSC, thus:
ΔGAB ¼ ηΔGAB þ ð1
ηÞΔGAB ¼ W
ΔGdiss ð8Þ
where ΔGdss = −(1 − η)ΔGAB. Thus, the total heat (Q) lost by
the system to its surroundings derives from two entropic
sources:
• the entropy (ΔSABX) exchanged between the system and
its surroundings, inescapably bound to the material trans-
formation A → B; and
• the entropy (ΔSC) created within the system and its sur-
roundings through the free energy dissipation required by the
Second Law, thus:
ΔS C ¼ jΔGdiss j=T ð9Þ
and depending on the thermodynamic efficiency at which the
transformation takes place.
Thus equipped, we may now examine how the thermo-
dynamic requirement for free energy dissipation plays out
dynamically in non-equilibrium rate processes.
It has been proposed5 and demonstrated3,4 that an intuitive
non-equilibrium thermodynamic framework for biochemical
kinetics inheres in the probability isotherm determining the
¶ Because ΔH frequently has a magnitude less than that of ΔG (as is the case for
diffusion, where ΔH is ideally zero), it is perhaps an unfortunate legacy that the
First Law’s ΔH usually takes precedence over the Second Law’s ΔG. Perhaps it’s
time for a change – after all, it’s ΔG that makes the world go round!
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probability ratio for forward and backward state transitions ( pf/
pb):
pf
ΔGdiss ¼ RT ln ð10Þ
pb
where ΔGdiss is the molar free energy dissipation of the tran-
sition. For any reaction mechanism, the probability isotherm
is manifest kinetically as the rate isotherm, determining a rate
ratio for forward and backward reaction, rf/rb:
rf
ΔGdiss ¼ RT ln ð11Þ
rb
These isotherms apply at all times to all chemical, osmotic
and chemiosmotic reactions, however complex, whether
unbranched6 or branched.7 They also proclaim the Second
Law’s requirement for non-equilibrium free energy dissipation
while, for isothermal processes, also proclaiming pari passu
the Second Law’s requirement for non-equilibrium entropy cre-
ation according to the relation given by eqn (9). Thus, chemical
reactants – through their involvement in non-equilibrium rate
processes – participate in both of the following entropic
phenomena:
1. Entropy exchange, through the differential entropy
content of reactants relative to products;∥
2. Entropy creation, through the forward to backward rate
ratio which obtains whenever there is a non-equilibrium differ-
ence between the forward and backward rates.
For given electrochemical boundary conditions the molar
entropy creation will be constant and independent of the level
of catalysis, while the absolute rate of entropy creation will
depend on the level of catalysis. We shall see that light quanta
involved in photochemical reactions participate in entropy cre-
ation but not in entropy exchange, having no entropy content
of their own to share or augment.
We are now in a position to clarify the widespread misun-
derstanding as to the supposed distinction between chemical
reactions that are said to be entropy-driven and those that are
said to be enthalpy-driven. The probability isotherm reveals
that chemical reactions are driven always and everywhere by
free energy dissipation and nothing else. The magnitude of
entropy exchange associated with any given reaction has absol-
utely no bearing on the essential requirement for free energy
dissipation. Perhaps the confusion arises from, for example,
the case of diffusion in which the enthalpy change (ΔH) is
ideally zero while the changes in free energy (ΔG) and bound
energy (TΔSX) are equal and opposite; such an example has
absolutely no enthalpy change to act as a driver, but the
bound energy change is not a driver either because it does not
result in entropy creation. Only with free energy dissipation do
we have entropy creation; entropy exchange does not have any
∥ All chemical reactants and products contain absolute entropy relative to zero
entropy content at the absolute zero of temperature. Net changes in their
entropy content during isothermal chemical reaction result in entropy exchange
with their surroundings as heat absorption or heat loss represented by the term
TΔSABX in eqn (4) and (5) above.
Photochem. Photobiol. Sci.

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direct quantitative bearing on the fulfilment of the Second
Law requirement for entropy creation through free energy
dissipation.
Fundamental misunderstandings
concerning the energetics of photo-
absorption
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In our view, three major errors have appeared over the years
concerning the energetics of photo-absorption occurring when
a chemical reactant, A, absorbs an incident photon – hν, where
h is Planck’s constant and ν is the frequency – to form an
excited state A* in the photochemical reaction
A þ hυ ! A ð12Þ
The three fundamental errors are as follows:
• Reaction (12) is assumed to be fully reversible according
to its representation as
ka
A þ hυ

)*

A* ð13Þ
ke
where ka is the rate coefficient for spontaneous absorption of
light quanta having frequency ν and ke is the rate coefficient
for spontaneous emission of light quanta having the same fre-
quency ν. The pedagogy of photo-absorption – including
exhaustive explication of the multiple possible fates of A* – is
quite disappointingly confused and variously incomplete in its
many manifestations. However, even a cursory reading of the
relatively exhaustive Appendix to Blankenship’s excellent
monograph on photosynthesis8 should alert the reader to the
casual naïveté inherent in such a formulation as appears in
reaction (13) above. Suffice it to say that the only conceivable
circumstance in which this formulation could take on any
possible validity might be in the case of resonance fluo-
rescence. As resonance fluorescence is such an exceptionally
limited possibility for the fate of a photon incident upon A
among other possible fates – such as reflection, refraction,
scattering, extinction, etc. – it does not even rate a mention as
such in Blankenship’s otherwise comprehensive section A.8
Molecular energy levels and spectroscopy ( pp. 267–278 and see
in particular Fig. A1.15 and associated text). This conceptual
error about the reversibility of photo-absorption is dealt with
more fully below.
• Incident light bears temperature. Light can be said to have
a ‘temperature’ only insofar as
○ its spectrum conforms to perfect black body
radiation,
○ its propagation is equal in all directions, and
○ its absolute intensity corresponds to that emitted by
a black body at the particular temperature in question.
Such light – of such specific absolute intensity and spectral
distribution – can be said to bear the temperature ‘signature’
of the emitting black body, but it cannot be said to bear within
itself that temperature, or any other temperature. In order for a
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physical entity to have a ‘temperature’ (i.e., a thermal poten-
tial), that entity must have a non-zero thermal capacity
(specific heat) in order to bear the heat within itself at the sup-
posed temperature. Light has no such thermal capacity.
• Incident light bears entropy. The alleged entropy com-
ponent of light is sometimes given as its energy divided by its
alleged temperature. At the ‘molar’ level (i.e., per Einstein of
incident radiation), the alleged molar entropy of monochro-
matic light of frequency ν would be given by
NA hν
Sν ¼ ð14Þ
TR
where NA is Avogadro’s number and TR is the alleged tempera-
ture of the monochromatic radiance.
While one can divide any quantity having the dimensions
of energy by the ambient temperature and declare the result-
ing quotient as ‘entropy’, the meaning of such a division is not
always clear. For example, division of both sides of eqn (5) by T
results in
1 1
ðΔGAB þ TΔSAB X Þ ¼ ðQ þ W Þ ð15Þ
T T
which yields
ΔGAB =T þ ΔSAB X ¼ ΔSAB X þ ΔS C þ W=T ð16Þ
reducing to
ΔGAB =T ¼ ΔS C þ W =T ð17Þ
In eqn (17) only one of the three terms – the created
entropy, ΔSC – has any entropic meaning; no entropic
meaning attaches to the terms ΔGAB/T and W/T just as there is
no meaning in the quotient of light energy and its supposed
temperature.
Thus, entropic attribution for light can be dismissed on
two distinct grounds:
i. As already argued, there is no possible temperature
attributable to light apart from the kind of temperature ‘signa-
ture’ which light of specific radiance, spectral distribution and
uniform omnidirectional propagation might bear in relation to
an emitting blackbody having the supposed temperature in
question. Consequently, the denominator of eqn (14) is a
meaningless, invalid entity.
ii. The energy contained in light – whether viewed at the
quantal level as hν per photon or at the molar level as NAhν per
Einstein – is all free energy; indeed, light may be correctly con-
sidered as being, rather than containing, free energy. This free
energy is literally free to raise the energy level of any atom into
which it might be absorbed by any amount up to the limit pre-
scribed by its frequency. In the case of resonance absorption
all the free energy is conserved in the excited state A* so long
as it continues to exist; in all other cases of absorption where
the energy of the excited state relative to the ground state is
less than that potentially available from hν, then there is
instantaneous free energy dissipation and, therefore, entropy
creation. There is no bound energy component of light – and
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Photochemical & Photobiological Sciences
therefore no internal entropy content – such as might partici-
pate in entropy exchange with chemical reactants such as A.
It is important to note that the relevant possible fates of A*
in this instance include reversion to the ground state via (a)
resonance fluorescence, (b) free energy dissipation as heat
(i.e., entropy creation) associated with either non-resonance
fluorescence or no fluorescence at all, and (c) engagement of
A* in chemical reaction.
All three of the above fundamental errors are contained in a
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chapter on solar energy conversion authored by Grätzel and
Moser9 which, in turn, seems to be based almost verbatim on
an earlier article by Porter.10 Similar suppositions were also
entertained by Ries and McEvoy.11
There is also a problem with the assertion that absorption
of incident light is equivalent to scattering the radiation in all
possible directions.9,10 Very simply, the light is not scattered at
all – not in any direction; it is annihilated – it ceases to exist.
Following annihilation of absorbed light beams or photons,
their energy becomes variously distributed through the atoms
and molecules upon which they have impacted, either dissi-
pated as heat or transiently stored in whatever excited states
have been produced in the electrons of certain atoms. Possible
productive fates of such photo-absorption include photochem-
istry in general and photosynthesis in particular.
Misapplication of the rate isotherm to
photo-absorption
The rate isotherm of eqn (11) for chemical reactions has also
been assumed 9,10 to apply to the photochemical reaction (12),
using a curiously notated formulation, thus:
Δμ ¼ RTln½1
ðj=JÞ ð18Þ
where j is the net rate of the reaction, J is the unidirectional
forward rate of reaction and Δμ is the molar chemical potential
difference between reactants and products. In fact, this
expression is identical to eqn (11); because the net rate, j, is
identical to (rf − rb), then it follows that [1 − ( j/J)] is identical
to rb/rf and so the molar free energy dissipation, ΔGDiss, is
equal but opposite in sign to Δμ, the molar free energy change
between reactants and products (Δμ is always negative for
spontaneous processes).
Relative to the self-evidently intuitive notation used in
eqn (10) and (11), the more operationally obscure notation of
eqn (18) arose from an equally non-intuitive expression of the
underlying photochemical reaction as:
J

*
A þ hυ )
A* ð19Þ
Jb
where J is the (unidirectional) forward rate and Jb is the (uni-
directional) backward rate.** The resulting formulation of the
** We wonder why such an exposition would notate the forward unidirectional
rate as J, i.e., not Jf, while notating the backward unidirectional rate as Jb.
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rate isotherm given in eqn (18) has the unfortunate effect of
making the backward rate implicit rather than explicit, thereby
veiling a problem that ultimately boils down to the questions:
1. Is the absorption of a photon represented in reactions
(12), (13) and (19) reversible?
2. May we treat the participants in these reactions as if they
were chemical species governed by the Second Law according
to the probability isotherm given in eqn (10)?
While the case of resonance fluorescence might afford a
loosely affirmative answer to the first question in a context irre-
levant to the present discussion,†† one should not be dis-
tracted from a fundamental difference between the energetics
of photons on the one hand and the energetics of chemical
reactants on the other; this difference impinges directly on the
answer to the second question.
Consider a single photon, hν, travelling through space until
such time as it might interact with matter. From such an inter-
action, the photon may emerge unscathed or it may vanish
forever, ceasing to exist. But, for as long as it exists, its
quantum of energy is conserved and immutably fixed at a
value of hν. A photon is thus energetically quite different from
a reactive chemical: a photon’s energy is absolute and inde-
pendent of its surroundings,‡‡ while the absolute energy of a
reactive molecule is essentially undefined and dependent on
its surrounding electrochemical field – only differences in
energy between reactants and products determine the bidirec-
tional progress of reaction according to eqn (11). This con-
sideration alone disqualifies the rate isotherm, developed for
thermal chemical reactions, from being applied to the inter-
action of light with matter in photochemical reactions.
It is bemusing to reflect on what possibly might have led to
this fundamental error in application of the rate isotherm to
photochemical reactions. A clue to identifying the offending
influence might possibly be found in the comprehensive over-
view of a particular aspect of the history and philosophy of
quantum theory explored in an important paper by Norton.14
We suspect that some scientists may have been unduly
beguiled by what is a patent overreach in the analogies drawn
between ideal gases, dilute solutions, suspensions, and
†† The phenomena of resonance fluorescence, stimulated emission and the grav-
itational bending of light are excluded from the present discussion as being irre-
levant to the particular issues being addressed here.
‡‡ This assertion is true in all situations of immediate practical relevance to the
issues discussed in this present perspective. However, the apparent behaviour of
light pulses in refractive media has given rise to the suggestion that this asser-
tion may not hold for refraction. The relevant literature is ambivalent on this
issue. On the one hand, a 2010 paper by Mansuripur12 develops a purported
resolution of the Abraham–Minkowski controversy by examining the behaviour
of a light pulse traversing a refractive model system represented in his Fig. 3
( p.2002) in which ( p.2001) “the entire pulse can enter the slab from the free
space on the left, then re-emerge into the free space on the right, without losing
any of its energy or momentum.” On the other hand, a 2017 review by Partanen
et al.13 deals extensively with the same issue but differs by proposing that “In
the relaxation process, a small amount of photon energy is dissipated into
lattice heat” without addressing the obvious question as to whether thermal dis-
sipation of photon energy occurs by annihilation (absorption) of photons, by
preservation of all photons with a red-shift, or by a combination of these effects.
Photochem. Photobiol. Sci.

Perspective
volumes of high-frequency electromagnetic radiation. It is
perhaps unfortunate that the set of “disanalogies” noted by
Norton (section 5.3 p.91) does not include the biggest ‘disanal-
ogy’ of all: the fact that the finitely many individual particles
of an ideal gas move by random Brownian motion involving
continual inter-particular collisions whereas the finitely many
individual quanta of light – in all conceivable contexts ranging
from Einstein’s famous thought experiments to the quotidian
falling of sunlight on terrestrial vegetation – travel in straight
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lines at the speed of light, free of any inter-particular col-
lisions, until such time as they interact with matter and so
succumb to any one of a number of possible fates.
These fates are manifold, including reflection, refraction,
scattering and absorption; the results of absorption are also
manifold and commonly include thermal heating, fluo-
rescence, phosphorescence and photochemistry. In all
instances of photo-absorption, the respective light quanta are
annihilated – they cease to exist; only in the special case of
resonance fluorescence can the annihilation be possibly con-
ceived as being reversible. It is therefore forbidden to treat any
manifestation of photo-absorption as a reversible reaction
subject to the thermodynamically determined laws embodied
in the probability isotherm and the rate isotherm applicable to
thermochemical reactions.
Metastability and implications for the
feasibility of photosynthesis
The inapplicability of the rate isotherm to a photo-absorptive
process such as reaction (12) becomes greatly magnified by the
metastability of photoexcited states, consideration of which
serves to clarify some essential bioenergetic principles relating
to the thermodynamics of photosynthesis.
Consider circumstances wherein a metastable excited state A*
can revert to the ground state by a chemical reaction such as:
kf
A* þ B

)*

AþC ð20Þ
kb
where kf and kb are the forward and reverse rate coefficients,
respectively. Here, the excited state enters the realm of thermo-
chemical reactions, governed thermodynamically by the prob-
ability isotherm and manifest kinetically through the rate iso-
therm. Reaction (20) thus affords a thermo-chemical mecha-
nism for reversion of excited state A* to ground state A that is
altogether distinct from, and independent of, any possible
reversal of the photochemical reaction (12).
If the metastable dwell-time of species A* in reaction (12) is
significantly longer than the time constant of diffusion-limited
binding of species A* to species B (or any intervening catalyst)
in reaction (20), then this would determine de facto irreversibil-
ity of reaction (12) in the face of a mechanism for reaction
(20). The practical consequence of this is that the de facto rate
ratio for reaction (12) would approach infinity, meaning that
its de facto Gibbs free energy dissipation would also approach
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infinity according to the probability isotherm. This would be a
thermodynamic impossibility: the total energy of a photon is
finite, determined by its frequency, and is the maximum differ-
ence of energy that the photon may confer on an excited state
relative to its ground state.
Thus, the portion of a photon’s energy conserved in the
excited state is available to drive any ensuing chemical reaction
that might be fortuitously located such that it can accept A* as
a chemical reactant. This, then, is the mechanism whereby
photosynthesis is able to drive backwards the highly exergonic
oxidation of reduced carbohydrate; so long as a mechanism
for the equivalent of reaction (20) exists at the entry points of
photosynthetic reactions, then sunlight provides unlimited
energy to drive the necessary reactions against the unfavour-
able gradients of their intrinsic and extrinsic probabilities.
The structured proximity of the equivalents of reactions (12)
and (20) in photosynthetic pathways means that the only prac-
tical fate of A* is to drive reaction (20) forward, while reversal
of reaction (20) is effectively crowded out by continuous photo-
excitation of A by sunlight via reaction (12). The metastability
of photo-excited states in such targeted catalytic environments
thus results in a de facto escape of Life on Earth from the
normal thermochemical constraints of the Second Law of
thermodynamics. This is another way of saying that neither
the probability isotherm nor the rate isotherm may be practi-
cally applied to reaction (12), particularly when a kinetically
faster chemical mechanism exists for the metastable photo-
excited state to revert to the ground state. Such chemical ‘kid-
napping’ of metastable intermediates may not be quite
Maxwell’s demon, but it effects a ratchet mechanism – a kind
of reverse escapement – facilitating the ascent of biochemis-
try’s Mt Improbable (carbohydrate synthesis) as a matter of
routine, operating continuously wherever the sun shines.
Although this perspective is far from being prescriptive in its
mechanistic implications, it seems significant that the elabor-
ate systems of photo-receptive antenna molecules feeding
photoelectricity via fast solid-state conduction mechanisms
into the photosynthetic reaction centres8 might function as
‘photon-clamps’ to clinch the required crowding out of poss-
ible reversal of the equivalents of reaction (20). This ‘clinching’
effect would be an unsurprising outcome of the very fast reso-
nance energy transfer processes15 that are possibly involved in
communication of photochemical potential from arrays of
antenna molecules toward the photosynthetic reaction centres.
Thus, atomically discrete injection of photo-energy from sun-
light into enzymatically structured metabolic pathways
achieves outcomes which the Second Law denies to thermo-
chemical reactions.
It cannot be overstated that the synthesis of glucose from
carbon dioxide and water via thermo-chemistry is a thermo-
dynamic impossibility: according to the probability isotherm
of eqn (10) glucose synthesis relative to glucose oxidation at 20
C has an adverse improbability ratio exceeding e1100, a value
beyond the numerical capacity of today’s personal computers.
Photosynthesis allows this massive chemical improbability gra-
dient to be overcome by the absolute certainty of continuous
This journal is © The Royal Society of Chemistry and Owner Societies 2020

Photochemical & Photobiological Sciences
discrete energy input via the irreversible absorption of solar
photons through structures integrated into the respective enzy-
matic pathways. It is thus important for the understanding of
photochemistry and photosynthesis that the historical error of
treating photo-absorption as a reversible chemical process be
identified and abandoned.
Conclusions
Published on 13 November 2020. Downloaded by Goteborgs Universitet on 12/7/2020 10:02:59 AM.
The thermodynamics and kinetics of atomic absorption of a
photon cannot be treated in the same manner as that used for
interaction between chemical reactants, despite earlier claims
to the contrary. A different perspective is suggested to assist
with understanding of photo-absorption and energy transfer
in photosynthesis.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
The Authors are grateful to Dr Phillip Brook-Carter of
Federation University Australia for reading and commenting
most helpfully on earlier drafts of this paper.
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