reviews
Chemical 1989. 89.
89 51147
(1989), 1, pp. 51147 51
Received January 13, 1988 (Revised Manuscript Received May 26, 1968j
Contents
I. Introduction 52
I I . General Mechanistic Principles 52
A. A Unified Formal View 52
B. The Radical Pair Mechanism 55
C. TripletTriplet and TripletDoublet Pairs 57
D. The Triplet Mechanism 59
E. Paramagnetic Conversion of Ortho and 60
Para Hydrogen
111. Experimental Methods 61
I V . Experimental Studies 64
A. In the Gas Phase 64
B. In the Solid State 67
Ulrich E. Steiner was born iii Backnang. Germany. in 1944. He
C. In Homogeneous Liquid Solutions 70 studied chemistry in Stungart. where he obtained his Dipknn degree
1. Thermal Reactions 71 in 1969. working with the late Th. Forster, and his Ph.D. in 1973,
working with H. E. A. Kramer. He habilitated in 1979 at Stungart
2. Photochemical Reactions 74 University. Before his appointment as Professor of Specbochem
3. Photoluminescence and 81 istry at Konstanz University in 1981. he held a Heisenberg leilow
Chemiluminescence ship. His general research interests encompass elementary mo
lecular reaction mechanisms in condensed phases. such as protm
4. Radioluminescence 84 or electron transfer, cistrans isomerization. and solvent effects
D. In Micellar Solution 86 on these processes. He is particularly interested in the role of
electron Spin during the elementary steps of photoelectron transfer
E. Interface Phenomena 94 reactions. His studies of magnetokinetic effects, dating back to
F. Biological Systems 96 1976, were initiated by the latter problem.
G. ReactionYieldDetected Magnetic 100
Resonance
H. Magnetic Isotope Effects 103
V. Theoretical Studies 106
A. Mechanisms in the Gas Phase 106
B. The Triplet Mechanism 109
C. The Radical Pair Mechanism 112
1. Historical Roots 112
2. General Formalism 113
3. Spin Motion 114
4. The Dynamic Probability Function 118
5. Assembling Spin Motion. Diffusion, and 119
Recombination
6. Treatments Based on Direct Solutions 122
of Stochastic Liouville Equations
7. TimeDependent Solutions of SLEs 129
D. TripletTriplet and TripletDoublet Pairs 129
E. ReactionYieldDetected Magnetic 134 Thomas Ulrich was born in Calw, Federal Republic of Germany, in
Resonance 1956. He studied chemistry at StuRgart University and graduated
in 1981. working with U. E. Steiner on the magnetokinetic triplet
F. Paramagnetic and Magnetocatalytic 137 mechanism. In 1982 he joined U. E. Steiner's group at Konstanz
OrtholParaHydrogen Conversion University. His doctoral research work was devoted to the time
VI. Conclusion 139 resolved investigation of magnetic field dependent radical pair ki
netics in reverse micelles. for which he was awarded the BYK prize
of the Herbert Quandt Stiflunq in 1988. He received his Ph.D. in
'Present address: llford AG. WFM 160.030. CH1701Fribourg. 1986. After 1 year of postdoctoral research work in Konstanz he
Switzerland. is now a research scientist with Ilford AG in Fribourg. Switzerland.
Konstanzer OnlinePublikationsSystem
00092665189107890051$06.50/0 Q 1989 American(KOPS)
Chemical Societv
URL: http://www.ub.unikonstanz.de/kops/volltexte/2008/4679/
URN: http://nbnresolving.de/urn:nbn:de:bsz:352opus46797
52 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
for magnetic field effects if these have any influence on on the golden rule formula (cf., e.g., Freed's review on
the transmission factor K . From this one may deduce radiationless processes60),which may be stated as
the principle that "diabaticity", i.e., a rather discon
tinuous change of the electronic wave function around kif = (2.rr/ft)C~mCl(i,mlHlf,n)1~6(Ei,m
 Ef,J (4)
m n
the barrier, is a requirement for magnetically sensitive
reactions. The symbols i and f denote initial and final electronic
For an appropriate theoretical treatment of such re states, combined with vibrational manifolds {m)and (n),
actions one has to go beyond eq 2 and use explicit respectively. The population probabilities p m of the
quantum theoretical expressions. The rate constant of initial vibrational states are usually expressed by
irreversible decay of quantum states is usually based thermal equilibrium values. Equation 4 should be seen
54 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
in combination with Figure 2. Here, however, only one H,t = H&r,R) + HOI1(r,ue,aN) HB(r,U,,qq,B) (8)
vibrational level of the initial state is indicated. It where H,”(r,R) designates the electronic orbital and
should be noted that the final vibrational manifold (m) vibrational contribution, Hon(r,a,,aN) is the nuclear and
must form an effective quasicontinuum at the energy electronic spin Hamiltonian including spinorbit cou
level of state li,m) in order that truly irreversible decay pling, and HB(r,a,,uN,B) is the Zeeman Hamiltonian
can occur. The states li,m) and If,n)are experimentally depending on the magnetic field strength (Bo for a
observable quasistationary states and correspond to the constant magnetic field or B1 sin(wt) for a microwave
eigenstates of a suitable Hamiltonian H,,,They become or radiofrequency magnetic field). The various elec
nonstationary through the perturbation H’, whereby the tronic states of the (ikJ manifold usually correspond to
rate of decay of the state )i,m)is proportional to the different eigenstates of the spindependent Hamiltonian
square of the corresponding coupling matrix elements H,” + HB. However, they are usually orbitally and
with final states If,n),and the &function selects those vibrationally degenerate, differing only in their elec
final states that allow for conservation of energy. tronicnuclear spin wave functions.
For most situations in which magnetic field effects The electronic spin manifold is usually realized as a
are observed scheme a of Figure 2 has to be extended molecular triplet state or as the spin manifold of
to a scheme of type b. Now the initial situation com paramagnetic reaction pairs such as of two triplets (nine
prises an electronic manifold (ik) of states with different spin states), triplet and doublet (six spin states), or two
electronic character, usually different spin states of the doublets (radical pair, four spin states). If H B con
same orbital origin (of course, it is understood that each tributes to Ho, magnetic effects are of the socalled
of the (ik) states is combined with a vibrational manifold indirect mechanism type (cf. Atkins and Stannardfl our
(mk},but this will not be always explicitly indicated). usage of the term is, however, more general). The in
Sometimes it is possible to define an overall decay direct mechanism is based on the requirement that the
constant of the ensemble (ikJ of initial states. Usually, coupling to the final manifold varies greatly among the
however, one is content to obtain timeintegrated yields states of the (ik} manifold (in many cases kif even cor
into different decay channels. Such yields are always responds to the adiabatic limit for one of the initial
uniquely defined and are the quantities usually ob states). Kinetic effects on the overall decay of the (ik}
tained from experiment. manifold ensue due to a magnetic recoupling, whereby
Within the framework defined by the scheme in the eigenstate basis {ik]B=O is transformed to the new
Figure 2b the MFE on the decay kinetics originates eigenstate basis (ik’JB.
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 55
As will be exemplified below, all the specific models mechanism is the production of a spincorrelated radical
of mechanisms accounting for kinetic MFEs may be pair, let us assume from an electronically excited triplet
classified as subcases of the general concept outlined state, yielding a radical pair with initially parallel
above. In order to do this systematically, the following electron spins. For energetic reasons the radical pair
distinctions are made. usually cannot recombine to yield an excited electronic
(I) Coupling to the (f,n)manifold: The matrix ele state but can only form a diamagnetic groundstate
ments H { f may be (a) time independent or (b) sto recombination product that is of singlet spin multipl
chastically modulated. In the reaction mechanism in icity. Thus, direct recombination of the initial radical
volving pairs of paramagnetic particles, time inde pair is spinforbidden. However, the spin state of the
pendence of H’usually requires fixed pair distances as radical pair is not stationary after separation of the two
in the solid state or solidstatelike situations. On the radicals, and spin evolution may eventually lead to a
other hand, particle pairs that are free to diffuse, as in singlet correlated state of the electron spins, so that
liquid solution, will undergo random encounters and in upon a next reencounter, the radical pair may recom
this way experience stochastic modulation of H ’. bine. This reaction (geminate recombination or cage
(11) Initial population and redistribution in the (i) recombination) competes with the final separation of
manifold. (a) The systems entering the ( i k ) manifold the radicals (escape reaction with the possibility of
may originate in states (ik’) (e.g., in pure spin states) forming products different from those of cage recom
corresponding to coherent superpositions of the Ho bination). The ratio of cage to escape reaction yields
eigenstates l i k ) , and it may be natural to describe the will critically depend on the rate of spin evolution,
kinetics in terms of populations of the lik’) , which will which, on the other hand, depends on an external
then exhibit a coherent time dependence determined magnetic field. Thus the reaction kinetics becomes
by Ho. Therefore, in order to calculate specific yields, magnetic field dependent.
a time integration of this motion in {ik’),space must be Comparing this model reaction mechanism with our
performed. The most adequate method to do this and
to also incorporate the effect of irreversible i
transitions is the application of stochastic Liouville
 f
previous general formalism, we note that the initial
electronic state manifold corresponds to four electronic
spin states of the radical pair, eventually combined with
equations (SLEs). a manifold of nuclear spin states if these are to be ex
(b) If rapid phase randomization occurs among the
lib) components and if the effect of Hrelis small, then
the decay of the ( i k )manifold corresponds to the i  
plicitly considered:
(ik} (RP: S, T+,To,TJ X {nuclear spin states)
(94
f transitions of kinetically isolated Ho eigenstates l i k ) ,
and the average reaction yields into various reaction VI)  (CP: Sol X (nuclear spin states) (9b)
channels are obtained as weighted sums of the indi
vidual ik contributions.

(c) If relaxation among the lik) due to Hrelcompetes
effectively with the i f process, the overall decay may
if2) (EP, SP) X (nuclear spin states) (9c)
There are two final electronic state manifolds corre
be described by a system of coupled kinetic equations sponding to cage products (CP) and escape or scavenge
for the populations of the lik) states. products (EP, SP), each combined with a manifold of

(d) If relaxation in the { i k )manifold is fast with re
spect to the i f decay, thermal equilibrium within the
( i k )manifold will be established, and the whole popu
nuclear spin configurations. Although the situation
represented by eq 9 is fairly general, one should note
that in a number of wellinvestigated cases, recombi
lation will decay as one quasistate with a rate constant nation products may be also formed in excited triplet
obtained by thermal averaging of the individual (ik)rate states (cf. section 1V.C).
constants. It should be noted that magnetokinetic ef The spin Hamiltonian Ho, which will be described in
fects will ensue under such conditions only if the energy more detail in section V, is usually a pure spin Ham
splittings within the (ik) manifold are at least compa iltonian. The part Hatdetermining the stationary states
rable to, or larger than, kT. Otherwise the (ik) states Hat = Hihf + Hex(Rad + HZ,el(B) (10)
will be equally populated and a recoupling of the lik)
in a magnetic field will not change the average decay comprises the isotropic hyperfine interaction (Hihf),the
rate constant. interradical exchange interaction (Hex),and the iso
We now turn to a consideration of special mecha tropic electronic Zeeman interaction (HZcl). Since the
nisms for magnetokinetic effects and establish their exchange interaction depends strongly on the inter
relation to the general framework described in this radical separation Rab, this contribution is modulated
section. by the diffusional motion of the radical pair. A rigorous
theoretical account of this effect is one of the most
B. The Radical Pair Mechanism difficult problems of radical pair theory.
Incoherent transitions among the eigenstates of H,,
The principles of the radical pair mechanism have are induced by Hrel,comprising anisotropic hyperfine
been explained in many original and review papers (cf. Hrel= H a h f + H&,,l(B) + HB.rot+ other terms (11)
Table 11, among which especially the treatise by Sal
ikhov et aLS2must be mentioned. Therefore, except for interaction (Hahf), anisotropic electronic Zeeman in
introducing its basic features, we are mainly concerned teraction spinrotational interaction (Hems, and
here with demonstrating the relation of this mechanism other interactions not explicitly mentioned. It must be
to the general formalism described in the previous noted, though, that spin relaxation in the radical pair,
section. i.e., the contribution of Ifrel,is neglected in most theo
A typical situation considered in the radical pair retical work on the radical pair mechanism.
56 Chemical Reviews, 1989, Vol. 89,No. 1 Steiner and Ulrich
T* T
I mselli R , rorel2i
01, 80
m o p t i c field

and T will he cut off from the conversion process, and
the To S process will he left at high field. If, however,
2 5 > Ehfono singlettriplet transitions will be possible
case 2 may lead to MFD curves with minima or maxima
and sign inversion due to the counteracting influence
of both mechanisms, each of which dominates in a
certain region of the magnetic field (case 1,2). Such
at zero field. A tripletsinglet level crossing will occur,
however, a t some higher field, allowing for tripletsin curves may he characterized by the field values B, of
glet transitions, which a t still higher fields are sup the maximum and B, of the zeroline crossing.
pressed again. This situation should he expected to give The case 3 situation would he ideally encountered
a type of resonance in the field dependence, with a with radical pairs subject to a moderate hut constant
maximum at a magnetic field of Bo = 2J/gfi,. exchange interaction ( 2 J > Ehfe). It is typical for a

Although, within the picture of coherent spin motion,
(T+,T_) S transitions are suppressed at high magnetic
fields, the stochastically modulated contribution of H,,
levelcrossing situation and may he characterized hy the
field values E,, corresponding to the maximum, and
AB, corresponding to the width of the resonance.
will cause incoherent (relaxational) transitions among
the spin suhstates. Their rate will, in general, also C. TrlpletTriplet and TripletDoublet Pairs
depend on the Zeeman splitting of the suhlevels. Sin
glettriplet transitions induced hy Hd, though generally A number of processes are known in molecular
much slower than those induced by HiW,may also in crystals and liquid solutions where pairs of two triplets
fluence the overall kinetics of chemical reactions if the or a triplet and a doublet interact by transferring
lifetime of correlated pairs is long enough to probe such electronic energy, involving a change of local multipl
58 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
icity. Thus, triplettriplet annihilation (in crystals also In terms of products of the individual triplet high
called triplet exciton fusion) may lead to higher excited field eigenstates IO), I+), and I) the coupled spin ei
singlets, a mechanism producing delayed fluorescence genstates of a TT pair are given by7
(eq 15).

T + T G (TT) S* + So (15)
IS) = ( 1 / ~ ) ( I O O )  I+)  I+))
The reverse of this process is also possible (socalled F+i)= (l/fi)(I+O)  IO+))
S* + So 2 (TT) T + T
singlet exciton fission: cf. eq E),
(16) IT,) = ( l / l h ( l +  ) I+))
whereby a sometimes “hot”,i.e., vibrationally excited,
singlet combines with an adjacent groundstate mole
cule to yield a pair of two triplets, which may eventually
separate. This process contributes to the quenching of
prompt fluorescence.
The interaction between a triplet and a doublet
species may lead to triplet deactivation with dissipation
of electronic excitation energy or, eventually, electronic
excitation of the doublet molecule (eq 17). Processes
of this type may be responsible for triplet quenching
in liquid solution or for mobilization of trapped charge

carriers in molecular crystals.
T + D e (TD) So + D (or D*) (17)
In the case of negligible intermolecular interactions the
Several excellent reviews on these processes and their pair energy eigenstates are simple products of the in
mechanisms have appeared.7J3J6i25Therefore, besides dividual triplet energy eigenstates. In general, these are
giving a short outline of the basic mechanism, we have not identical with the pair spin eigenstates of eq 20, but
as our main object its correlation with the general linear combinations of these. One should note, however,
mechanistic view introduced in section A. that in case of D1 = D2 the spin Hamiltonian is sym
MFEs on the kinetics of the processes described by metric with respect to exchange of the triplet spin op
eq 1517 are of the indirect type. The initial state erators S1and S2,so that the energy eigenstates may
manifold (ik]consists of the set of coupled spin states be classified as symmetric or antisymmetric, respec
of the pair (nine states in the case of a TT pair and six tively. As follows from eq 20, the pair triplet states are
in the case of a TD pair). The way the {ik] states are the antisymmetric ones, whereas the pair singlet and
coupled together to energy eigenstates depends on the quintet states are symmetric with respect to spin ex
strength and direction of an external magnetic field. On change. This separation will be valid at any field
the other hand, the reactivities of the pairs into various strength so that, in this case, the singlet pair state may
product channels are governed by the principle of to be distributed over a t most six energy eigenstates.
talspin conservation. In terms of our general classi In comparison to their width, determined by the
fication scheme the mechanistic type according to which lifetime of the correlated TT or TD pairs, the eigens
these effects are usually treated corresponds to the tates of Hoare normally clearly separated. Thus, overall
Ia/IIb case or sometimes to the Ia/IIa case. reaction efficiencies ym and YTD may be determined
The interaction Hamiltonian H’, inducing reactions (case IIb) as the average of contributions of single en
of the pair, is usually considered as constant during the ergy levels, for each of which the reaction rate constant
lifetime of the pair and treated semiempirically by at is proportional to the singlet character Sior doublet
tributing firstorder rate constants to the spinallowed character Di, respectively, of the Ho eigenstate:
reaction channels.
1 ksSi
Interactions contributing explicitly to Ho are y n= c
9 k1 + ksSi
(21)
Ho = HZFS + He, + HZ(B
1
(18)
where HZFsis the zero field splitting Hamiltonian ac
counting for intramolecular spinspin and spinorbit
interaction in the triplet molecules. It is conveniently
expressed by using the ZFS tensors D1 and D2: Here, ks and k D are the reaction rate constants for
HZFs = S1’D1’S1 + S,.D2.S2 (19)
pure singlet or doublet pairs, and kl is the rate constant
of dissociation of such pairs. The expressions are ki
In the case of a doublet in the pair, one of the ZFS netically obvious.
terms should be substituted by the isotropic hyperfine This kind of treatment is due to Merrifield.71 It
interaction, which, however, is of lower order of mag follows from eq 21 (analogous conclusions may be drawn
nitude. from eq 22 for TD pairs) that redistribution of singlet
The intermolecular electron exchange interaction He, character Si over the various eigenstates lik) as occurring
is often neglected in theoretical treatments of TT and under the influence of a magnetic field will change the
TD pairs (for exceptions cf. ref 69 and 70). Also ne overall efficiency ym of the reaction. One may draw
glected is intermolecular spinspin interaction (not the general conclusion that ym is larger the more
explicitly appearing in eq 18). The final term, H z ( B ) uniform Siis distributed among the eigenstates. This
is the electronic Zeeman Hamiltonian. may be demonstrated with the extreme cases Si=
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 59
TABLE 2. Distribution of Singlet Character over TTPair that a resonance minimum is detected when the orien
Energy Eigenstates tation of the crystal is swept over such a position (low
no. of energy eigenstates field resonances).
magnetic carrying singlet character In high fields the singlet character is generally dis
field D1 DI Di f Dz tributed over two energy eigenstates:
Bo = 0 3 9
Bo IZFS <3‘ <9a
Bo >> ZFS 2 (1): 2
“Precise value depends on field orientation; in solids extrema
are found at directions called “lowfieldresonances”. In solids at
special field orientations, where the socalled ’highfield
resonances” are observed.
spin function is odd and the rotational part of the wave TABLE 3. Acronyms in Use for Various Types and
Detection Modes of Maenetokinetic Effects
function must be even ( L = 0, 2,4, ...). Thus the lowest ~~ ~
rotational states of the two forms are separated by one acronym meaning ref”
rotational quantum of about 100 cml. A t cryogenic ADMR absorbancedetected magnetic resonance 88
temperatures the para form can be enriched on a cat CIDEP chemically induced dynamic electron 84, 85
polarization
alytic surface. In the absence of catalytic materials CIDNP chemically induced dynamic nuclear 86, 87
establishment of the ortho/para equilibrium is quite polarization
slow, even at elevated temperatures. Catalytic con CIDNPNR CIDNPdetected nuclear magnetic 89, 110
version may be effected by two mechanisms. In the resonance
DFODMR delayedfluorescence ODMR 90
dissociative mechanism Hz molecules are dissociated FDMR fluorescencedetected magnetic resonance 91, 92
due to the catalytic activity and recombine at random. MARY magnetic field modulation of reaction 93
This mechanism will not be of interest in this review. yields
The other mechanism is based on the interaction of MIE magnetic isotope effect 9496
hydrogen molecules with paramagnetic centers either MODS magnetooptical absorbance difference 97
spectroscopy
in the gas phase, in liquid solution, or on solid surfaces. MODSC magnetooptically detected spin 98, 309
Except for a recent paper by Sugano and Ilisca81 (cf. conversion spectroscopy
section V.F), it has been assumed that the basic in ODESR optically detected electron spin resonance 99
teraction responsible for the para/ortho conversion is ODMR optically detected magnetic resonance 100105
the inhomogeneous dipolar magnetic field due to the RYDMR reactionyielddetected magnetic 106
resonance
paramagnetic spin, which is experienced with different RYDMAR reactionyielddetected magnetic 107
strength and direction by the two nuclei in a hydrogen resonance
molecule. Therefore they will undergo different pre SPDL spindependent luminescence 108
cessional motions and eventually change their relative TDR tripletdoublet resonance 109
TTR triplettriplet resonance 109
spin alignment.
In this respect the mechanism is quite analogous to a References denote first users of these acronyms or pioneers in
the change of electron spin in a radical pair, which is developing the respective mechanisms and experimental tech
nioues.
also due to different local magnetic fields at the sites
of the two electron spins. Essential differences, how
ever, lie in the fact that in radical pairs it is a constant
intramolecular hyperfine coupling that governs the I I I . Experimental Methods
different motions of the two electron spins, whereas the
two nuclear spins in the H2 molecule are reoriented due The various mechanisms described in the last section
to an intermolecular anisotropic hyperfine interaction are detectable in rates and yields of particular chemical
with a colliding paramagnetic particle. Another fun reactions or related physical processes. A great variety
damental difference is that the different spin states of of experimental methods have been applied to induce
a radical pair are degenerate within the width of the and detect such changes. In connection with these a
coupling interaction, whereas in the ortho/para hy number of acronyms have been created that have been
drogen case the energy difference is on the order of 100 more or less accepted in the literature. These are
cml. This requires energy exchange with other degrees collected in Table 3. Their number may give an ex
of freedom during a collision with the paramagnetic aggerated impression of diversification in the field. It
particle. The latter point is essential and was first taken should be noted, however, that different terms are in
into account by Wigner.82 use for rather similar methods.
External MFEs on catalytic ortho/para hydrogen Four main groups of techniques may be distin
conversions have so far been only observed on magnetic guished:
surfaces (socalled magnetocatalytic effect; cf. the review (i) Chemical reactions conducted in stationary mag
by SelwoodZ6). Although the mechanisms of these netic fields may produce spinpolarized products. Spin
processes are not yet fully understood, it seems to be polarization of nuclei (CIDNP) or radical electrons
clear that the mechanism is of the indirect type. The (CIDEP) is detected by magnetic resonance during or
initial state manifold (ik]has to be constructed from the immediately after the reaction. A particular way of
combined states of para hydrogen rotational states and detecting chemically induced spin polarization might
the electron spin of the paramagnetic centers: even utilize the generation of radiofrequency maser
activity.”l Chemically induced magnetic polarization
(ik) = {PHz( L = 0, 2, ***I]X (Sparamagn] (34) is an enormous field of its own and will not be covered
in this review. However, selected references will be
The interaction with the ortho hydrogen manifold made to CIDMP work (this term includes both nuclear
occurs by the mechanism mentioned above. The in and electron spin polarization), which is of interest in
teraction operator H’ is randomly modulated according relation to our topic.
to the statistics of the collisions. The corresponding (ii) The overall change of yields and kinetics of
theory would be of the Ib/IIa type. As has been pointed chemical and related physical processes due to the effect
out by I1iscas3 (cf. section V), one must assume that of a static magnetic field may be directly detected. The
large deviations from equilibrium are generated in the magnetic field dependence of such effects has been
(ik]manifold due to the adsorption/desorption kinetics referred to as a MARY “ s p e ~ t r u mparticularly
”~~ when
of H2 molecules on the surface. It is mainly the mag discussed in relation with RYDMR spectra (cf. below).
netic effect on this polarization that is responsible for The MARY acronym is, however, not generally used for
the kinetic effects of the magnetic field on the overall magneticfielddependent reaction yield effects. Vari
para/ortho conversion rate. ous physical or chemical parameters, to be surveyed
62 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
below, have been used to monitor the MFD of reaction Bitter National Magnetic Laboratory of MIT1l9or the
yields. Some of these modes of detection have been HighField Magnetic Laboratory of Grenoble.lZ0Thus
assigned special names such as MODSC98,309 for both it is understandable that not many investigations of
luminescence and absorption detection, MODSg7for chemical reactions in ultrahigh magnetic fields have
modulated absorption spectroscopy, and TTR or been reported.
TDRIOgfor photoconductivity detection in molecular The RYDMR techniques require that a considerable
crystals (cf. Table 3 for the meaning of these acronyms). fraction of resonant spin flips take place during the
(iii) Different nuclear magnetic moments of different geminate periods of paramagnetic particle pairs, which
isotopes may cause differences in reaction rates and are typically in the submicrosecond time regime. Thus
yields, which may eventually lead to a selective dis the B1 field must be on the order of 1 G or larger,
tribution of different isotopes over the products of a meaning that much higher microwave powers are nec
reaction. These effects constitute the field of magnetic essary than in conventional ESR spectroscopy. Oth
isotope effect^.^^^^ erwise RYDMR spectrometers are very similar to ESR
(iv) The effect of a static magnetic field on reaction spectrometers, however without using the absorbed
kinetics and yields may be modified by the absorption microwave power for monitoring the resonance. For the
of resonant microwave radiation, offering the possibility usual Xband technique (9.5 GHz) normal ESR cavities
of measuring the magnetic resonance spectra of par with facilities for optical detection are in use. The
ticular reaction intermediates responsible for the MFE. required microwave power is produced by a clystron
This method is called reactionyielddetected magnetic valve or a Gunn diode combined with travelingwave
resonance (RYDMR).lo6 Many subcases are distin tube amplifiers. Representative examples of power
guished by special terms. Especially for luminescence specifications are 5ps pulses at 350 WlZ1or 1.6ps pulses
detection (ODMR) a number of equivalent terms are at 2000 W.lZ2However, much shorter pulses of about
in use (FDMR, ODESR, SPDL; cf. Table 3). The ab 60 ns, still with B1= 1.5 G, correspondingto a 7r/2 pulse
sorption method analogue to ODMR is ADMR.88 The intensity, have been also realized in applications of
method of CIDNPNR89J10is also a RYDMR subcase, timeresolved RYDMR in a spinecho spectrome
since it uses resonant radiofrequency fields during a ter.1237124
reaction, the effect of which is detected via CIDNP in RYDMR has also been applied at low fields with
the diamagnetic products. frequencies in the 2501700MHz region where powerful
In the following we provide a short survey of the frequency generators of about 50 W are available. As
various methods used so far to monitor magnetokinetic in ESR, a t these frequencies special cavities, e.g., a
effects and give some basic information on magnetic stripline cavitylZ5or a splitring r e s o n a t ~ r , ' ~have
~J~~
equipment applied in these investigations. to be used.
1. Magnets and Microwave Equipment 2. Chemical Analysis
Magnetic fields up to 0.1 T (1000 G) may be con If MFEs are borne out in product yields of irrevers
veniently produced by a pair of Helmholtz coils. These ible reactions, conventional methods of chemical
have the advantage that they are inexpensive, the sam analysis may be applied after the reaction has been
ple space is easily accessible from all sides, and, fur terminated. Thus MFEs in gasphase reactions have
thermore, the magnetic field may be rapidly modulated been analyzed by using gas chromatography,lZ7mass
to allow a more sensitive detection of the effects (for spectrometry,lZ8or a combination of b0th.l" Magnet
applications cf., e.g., ref 112 and 113). icfielddependent yields of reactions in solution have
Permanent magnets, which can provide fields up to been analyzed by vaporphase chromatography after
1.5 T, are practically not in use since their field is not suitable pretreatment of the reaction mixture^.^^^^^^
variable. In this context it may be of interest, however, Application of thinlayer ~ h r o m a t o g r a p h y l ~and
~  l of
~~
that microscopic ferromagnetic particles have been used highpressure liquid ~hromatography'~~ has also been
for magnetic modulation of chemical reaction yields.l14 reported in relation with the detection of magnetic field
For magnetic fields up to 4 T, electromagnets are effects.
~ 0 n v e n i e n t . l ~Smaller
~ types of about 50kg weight In favorable cases the reaction yield may be obtained
usually can provide magnetic fields up to 1T between from an in situ analysis of the reaction mixture, as has
flat poles of 12cm gap. With tapered poles and gaps been applied, e.g., by Molin and c o  ~ o r k e r s , who ~~~J~~
of 0.51 cm, field strengths up to 2 T are attainable. used lH NMR and 19FNMR to detect magnetic field
Electromagnets of several hundred kilogram weight are effects on the yield of thermal radical reactions per
necessary for magnetic fields of about 2.5 T with 23cm formed directly in a NMR sample tube. Even more
gaps and up to 4 T with about 0.5cm pole gaps. favorable are cases where the reaction can be followed
Pulsed fields up to 7 T, which are approximately by continuous probing of some characteristic physical
constant over a period of about 3 ms, have been pro parameter (cf. section 4).
duced by discharging a capacitor through a sole Conventional chemical analysis may be also applied
noid. 116,772,773 to determine the MFD of the yield of shortlived tran
The field region up to 15 T is accessible by use of sient species, if it is possible to trap these species in
superconducting magnets,l17 whereas ultrahigh fields relatively stable products. Examples are the use of spin
u p to 25 T are realized by disk coils, socalled Bitter traps for radicals139and of suitable scavengers of singlet
magnets,l18 with an electrical power consumption of o~ygen.'~~J~~
several megawatts, necessitating very efficient water Finally, the interesting case of a MFE on the mo
cooling. Instruments of this type are usually available lecular weight distribution obtained in emulsion po
only in special highfield laboratories, e.g., the Francis lymerization must be mentioned.142
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 63
i: rl
In the case of reversible photoreactions, photo
stationary states are established under continuous il
lumination. Although the stationary concentrations of
shortlived transients (such as triplets or radicals) may
be quite small, modulation techniques may provide the
required sensitivity to record absorption signals of these
species and determine the MFD of their stationary
concentrations. Thus, Bube et a1.112 using two CW
C I
lasers for excitation and probing and applying square
120 s I div wave modulation of the magnetic field together with
phasesensitive detection of absorption were able to
Figure 8. Detection of MFE by continuousphotolysis in a measure the MFD of anthracene ion formation in the
flowthrough apparatus, for example the photoreduction of thi
onine (6s) by piodoaniline in methanol (from Schlenker and reaction of singlet excited anthracene with diethyl
SteinerlS2). The diagram shows Y / t traces of (a) the absorption aniline.
signal a t fixed wavelength, (b) photolytic light intensity, and (c) The MODS technique of Hoff et al.97is based on the
magnetic field strength. same principle.
If kinetic MIEs occur in irreversible chemical reac The application of photostationary modulation
tions, this results in magnetic isotope enrichments. So techniques for probing the absorption of radicals and
far, reliable results have been reported for the magnetic electronically excited triplets is rather unusual. The
isotopes 13C and 170only. Enrichments of 13C have standard method for determining the yields and ki
been detected by 13CNMR= and from 13Csatellites in netics of such intermediates is flash photolysis. The
lH NMR ~ p e c t r a . ' ~ ~ J ~ ~ conventional flash technique, however, is rarely used
Enrichments of 170have been detected from mass for the investigation of magnetic field effects (cf., e.g.,
spectroscopic data of oxygen developed in endoperoxide ref 156), probably because most conventional flash
t h e r m ~ l y s i s or
l~~from IR data based on the different equipment uses a close coupling of cuvette and flash
carbonyl frequencies of R2C160(1717 cml) and R2C170 lamps, making it difficult to apply a magnetic field to
(1705 cm1).148 the sample. This problem does not arise with laser flash
excitation, where very small excited volumes can be
4. Rates and Quantum Yields from Photostationary probed even in magnets with difficult access to the
Kinetics sample space.
Whereas singleshot laser techniques usually provide
In many cases the rates of photoreactions resulting only a rather qualitative picture of the MFD, the ac
in permanent product formation can be conveniently curacy can be greatly improved by the use of signal
followed in continuousillumination experiments. The averaging and timeselective absorption sampling. In
usual method, as for the determination of photochem the latter method two laser pulses are applied, where
ical quantum yields, is to follow the reaction by optical the first, strong pulse serves to excite the sample and
absorption spectroscopy, either by continuously re the second, weaker pulse probes the transient absorp
cording at a fixed wavelength or by recording complete tion at a fixed delay time.157J58This method has been
spectra at certain intervals of irradiation perfected by Treichel et al.,159yielding an excellent
The reproducibility of photokinetic slopes in different reproducibility of the MFEs (cf. Figure 19).
runs is often a limiting factor in the accuracy to which The other efficient method to reduce the signal
MFEs can be determined. In order to get more direct scatter, which is mainly due to a variation of single
information on the MFD of photochemical quantum pulse energies, is online processing of many repeated
yields, Schlenker and Steinerls2 developed a special transient signals by the use of microcomputer facilities.
technique whereby the solution is irradiated in a flow Laser flash equipment working on this principle has
through cuvette. Opening or blocking the irradiation been described by Ulrich et a1." An interesting novel
light produces steplike changes in the absorption sig development has recently been reported by McLau
nal, which is continuously recorded at a fixed wave chlan and coworkers.121 They use a series of pulses
length in a second flowthrough cuvette positioned in with the magnetic field on and off in alternation for
a UV detector. The height of the steps is proportional successive laser pulses, so that by suitable data pro
to the quantum yield of the reaction. Switching on and cessing they achieve a realtime differencing of the
off of a magnetic field at the irradiation cuvette during signal intensity with respect to the magnetic field.
the irradiation periods produces corresponding steps in Their spectrometer may be used for measuring the
the absorption signal trace, from which the MFE on the MFD of reaction yields as well as for recording RYDMR
quantum yield is directly obtained. In Figure 8 an spectra.
example of a MFE detection by this technique is shown. So far, the time resolution of laser flash spectroscopy
Other detection methods for continuously following as applied to investigate MFEs has been restricted to
magneticfielddependent reactions have made use of the nanosecond time regime. This usually does not
variations of pressure in gas mixtures130or of thermal suffice to yield a good time resolution of the geminate
conductivity changes in cases of hydrogen ev01ution.l~~ recombination kinetics of radical pairs in lowviscosity
The latter method is also generally used in order to solutions. Magneticfielddependent kinetics is, how
64 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
ever, particularly clearly borne out in micellar161J6zor CS2,glyoxal) have been also reviewed in some detail by
microemulsion s o l ~ t i o n . ~ ~ ~ J ~ ~ Kuttner et ai.zio and by Lin and F ~ j i m u r a .Many
~ ~ of
the observations listed are due to magnetic field effects
6. Luminescence on radiationless decay and not accompanied by rever
sible or irreversible chemical change. Since they appear,
Luminescence may be detected very sensitively and however, as a phenomenological and mechanistical
very accurately and is an ideal method for determining unity with truly chemical effects, we have included
MFEs if electronically excited products are formed in them, too, the more so as any process determining the
the magneticfielddependent process. The simplest lifetime of an electronically excited state must be re
technique is to measure stationary luminescence in flected in the quantum yield of a competing photo
tensities as a function of the magnetic field strength. chemical reaction from this state.
Many examples of MFE detection using this method A typical feature of MFEs in the gas phase is that
are provided in section IV for solidstate, liquid, and they are usually found with small molecules, which are
gasphase systems and in flames. characterized by a sparse density of rovibrational states.
Luminescence may be excited optically by highen Thus irreversible transition to the final state manifold
ergy radiation or may result from chemiluminescent or often requires collisions to provide an effective contin
electrochemiluminescent reactions. In the case of small uum. Such a mechanism will become evident in the
MFEs it has been advantageous to modulate the mag pressure dependence. Magnetic fields may influence
netic field and use phasesensitive detection of lu either the pressuredependent or independent part of
minescence. In this way Frankevich and co~orkersl'~ the decay rate. Other important mechanistic distinc
were able to achieve a relative sensitivity of better than tions arise from the magnetic moment of the initial
5 X lom5,which allowed them to resolve the MFD of state. Thus paramagnetic triplet or doublet states may
luminol chemiluminescence, showing a maximum effect show magnetic field dependence even in multiplicity
of only 0.15% at high fields. conserving processes (Iz, NOz) whereas the magnetic
Timeresolved MFEs have been observed in radio field sensitivity of excited singlet states is usually re
luminescence applying the singlephotoncounting lated to intersystem crossing (ISC) processes (glyoxal).
technique.lW" Particularly high reproducibility of the
MFEs is obtained if the accumulation of singlephoton 1. Photoluminescence Studies
statistics is made intermittently with periods of mag
netic field on and off, so that longtime drifts cannot The first case of magnetic fluorescencequenching was
wipe out the MFE.16g,761 reported by Steubingla0in 1913 and further corrobo
Luminescence methods have also been applied to rated by a number of later inve~tigations.'~~l~~ The
probe the yields of shortlived products formed in their magnetic quenching effect in iodine is due to a mag
ground states. The method used was a twostep la
serexcited fluorescence detection, where the second
(probing) laser pulse excites the product and the inte

neticfieldinduced predissociation of the 3110+ustate
(note that the "fluorescence" is a 3110+u X'Z+ tran
sition), which was first suggested by Franca and
gral of the resulting fluorescence pulse is a measure of Grotrianla4 and substantiated by experiments of
the concentration of this species. The kinetics of its Turner.ls5 According to van VleckZz3the magnetically
formation and decay may be determined from a variable induced transition leads to a nonbonding 3110+u state,
delay of the second laser pulse.170171 which is forbidden in the absence of a magnetic field
(cf. section V). Investigating details of the excitation
7. Photocurrents wavelength and magnetic field dependence, Degenkolb
et al.lss and Chapman and Bunkerla7were able to con
If a magneticfieldsensitive reaction mechanism struct the potential curve of the dissociative state by
produces charge carriers in a medium of low selfcon evaluating the FranckCondon factors for magnetic
ductivity, current measurements are an obvious method predissociation of the various vibrational levels of the
of investigation. So far little use has been made of such 3110+ustate. According to a suggestion by Vigue et al.,lW
techniques in s o l ~ t i o n s There . ~ ~ are,
~ ~ however,
~ ~ ~ ~ ~ ~the
~ perturbing state should be a l u state, to which also
more investigations applying photoconductivity mea a rotational predissociation in the absence of a magnetic
surements for detecting the MFD of processes occurring field can occur. That this is in fact the case was cor
in the bulk (cf., e.g., ref 173 and 174) or at surfaces (cf., roborated by the ,detection of a magneticfieldde
e.g., ref 175 and 176) of organic molecular crystals. pendent weak circular polarization of the emitted iodine
Other examples may be cited from the field of inorganic fluorescence.
semiconductor^.^^^^^^ Another case of magneticfieldinduced radiative
dissociation of electronically excited Hgz reported by
Franck and Grotianls4was not confirmed in later ex
I V. Experimental Studies periments. lgl
Proceeding from iodine to the triatomic examples
A. In the Gas Phase NO2, SOz, and CS2, the conditions and mechanistic
details of the magnetic effects become more complex.
Magnetokinetic effects in the gas phase have been In NO2, which was investigated by Butler et a1.,192194
observed in photoluminescence, in light emission from a magnetic field enhances the collisioninduced
flames, and in irreversible photochemical change. A fluorescence quenching. The magnetic field dependence
survey of these is given in Tables 4 and 5 . Most work of the fluorescenceyield (cf. Figure 9) may be described
has been done on the photoluminescence of small by a Lorentzian line shape centered at Bo = 0. How
molecules, the most prominent cases of which (I2, N02, ever, the halffield values and the modulation depth of
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 65

due to reduction of line reversion by Zeeman effect
OH magnetic enhancement of A22+ X211 emission from H2 (or C3H8)/02flames Haya~hi~~~,~~'
HPO magnetic quenching of A'A" X'A" emission from (NH4)2HP04in H2/02 Wakayama et aL218
SnH
NO
flames

magnetic quenching of 41: X2111/2emission from SnC12in H2/Ozflames
magnetic quenching of microwave discharge afterglow from N(4S) + O(3P)  Fukuda et aL2I9
NO(B211,)

reaction
cis2butene trans2butene"
SO2 + C5H12  hv HS02C5Hll
effect
increase of rate by 30% in magnetic field of 8.5 T
MFE on quantum yield 30% for Bo > 0.2 T
ref
Falconer and Was~erman'~'
Sorokin et al.lB
DZCO  hv
OHCCHO  hv
cycloheptane  hv

D2 + CO
H2C0 + CO
6heptenal
MFE on quantum yield +6% at 0.4 T, 0% a t 0.8 T
MFE on quantum yield 15% at 0.3 T and p = 0.05 Torr
magnetic decrease of quantum yield 3.6% at 0.6 T
Sorokin et al.12s
Sorokin et a1.220
Stich et a1."
Csz('II,) 
2cs(2P3,z)
CIDNP in the gas phase
predissociation leads to selective magnetic substate
populations of Cs atoms
Dushkin et al.221
Kat0 and OnomichiZz2
the fluorescence yield by the magnetic field are of a must go along with a reduction of the intersystem
rather erratic wavelength dependence. It is assumed crossing efficiency. The fluorescence lifetime shows an
that the magnetic field couples the fluorescing doublet interesting pressuredependent magnetic field effect.'%
state to some intermediate state that is itself coupled At low pressures the lifetime increases by a magnetic
to a continuum via the collisions. The nature of the field, which has been explained by a magnetically in
intermediate state is not clear. duced Douglas effect. The magnetic field is assumed
In SO2 fluorescence and phosphorescence have been to mix the electronically excited BIBlstate with rovi
observed to be magnetically q ~ e n c h e d . ' ~ ~The
, ' ~fact
~ bronic levels of the XIAl ground state. Whereas at low
that the phosohorescence lifetime is magnetic field in pressures this mixing just dilutes the oscillator strength
dependent1% indicates that fluorescence quenching of the electronically excited state, at higher pressures
66 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
S1 T + T, threshold of
SIvibrational energy
Klein et al.,237,238
Albrecht et al.239
Arnold246
anthracene/ tetracene
(a,P, P, VUV)
DF after Xray preirradiation
DF, spectral separation of host
T + D+ SI + D+ Ern and Merrifieldm
T, + T T ST (heterofusion) Groff et al.,286v289Chabr et al.257
(host/guest) and guest
9.10dichloroanthracene DF, PC: orientation dependent T+TSl KotaniZs7
9,lOdiphenylanthracene
tetracene
DF
PC
resonances
T + T Si. 
T + D+,, Sl + D+mob
+
Me~ifield~~~
MFE on efficiency of charge Frankevich and Balabanov,229
carrier production Frankevich et aLZ3O
PC, highfield resonances
PC with hole injection 
triplets involved
S1 T + T o r T + T
depending on exciton
 Delannoy and Schotti7'
SI, Geacintov et al.,233F r a n k e ~ i c h ' ~ ~
density
PF, MFD, and highfield resonances SiT+T Merrifield et aLZs
PF, temperature dependence Si+T+T Geacintov et
PF, variation of excitation intensity fission, superimposed by Pope et a1.260
fusion at high exciton
densities
PF, variation of excitation wavelength fission and fusion Groff et a1.261J62
PF Moller and Pope263
EL, h+ and e injection
aparticle scintillation, temperature
SIT+T
T + D+ So + D+
fission and fusion effects
Kalinowski and GodlewskiZM
Geacintov et a1.2"
dependence
tetracene/pentacene PF, spectral separation of host homo and heterofission Geacintov et
(host/guest) and guest emission
PF and DF, a t high excitation heterofusion Kalinowski and Godlewski2@
intensity
tetracene/2,3benzocarbazole PF, high dopant concentration geminate T + T fusion: Arnold et al.267f268
(host/guest) "exciton caging"
pyrene DF T+T+Si Yarmus et
fluorene/pyrene (host/guest) DF, ESR T + T Si, (TT)ESR PekcanZ7l
detected
aperylene, Pperylene PF, MFD of excitation spectra determination of fission Albrecht et
threshold; blue shift in
excimer forming aperylene
rubrene DF T+TS? Frankevich et al.272
poly(Nvinylcarbazole) (with PC and PF from exciplex, both charge carrier generation Okamoto et al.2'3
dimethyl terephthalate as with positive MFD more efficient from singlet
dopant) exciplex
anthracene/dimethylpyro PF and DF Ag mechanism in Wannier Frankevich et
mellitimide EDA complex
DF. multiresonant MFD 
exciton and T + T .SI
T + T Si, level crossing of Lesin et a1.275
different M, levels
(exchange interaction)
anthracene/ pyromellitic PC, detailed Bo and orientation T + D+tr So + D+mobr Ziegler and Karl"
dianhydride EDA complex dependence complete ZFStensor
evaluation
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 69
TABLE 6 (Continued)
compd
Pt(phtha1ocyanine)
MFdependent observationo
P, decay at 4.2 K, Bo up to 10 T 
mechanism suggested
T + T S1,highfield maximum
of MFD due to 8.5cmI ZFS
ref
Kaneto et aLns

in the framework of Merrifield's model (cf. section 11).
The rate constant of the T + T S1process in a ran
dom encounter (TT) pair will be largest if the singlet
pair state l(TT)is distributed most uniformly over the
eigenstates of the pair spin Hamiltonian. This effect
is borne out in the MFD of the delayed fluorescence (cf.
Figure lo), typically showing an increase at low fields,
a sign conversion for fields comparable to the ZFS, and
0.9c I i a negative branch at high field. Several maxima in the
s s DFMFD curve may be formed if the (TT) pair states
0 .a
0 I 2 3 4 of different multiplicity are split in zero field. Such
MAGNETIC F I E L D ( k O @ )
exchange splitting is usually negligible for plain aro
Figure 10. Experimental MFD curves of delayed and prompt matic compounds. But evidence for its effect has been
fluorescence in a tetracene crystal. The field wm oriented at  2 O O provided with crystals of the pyromellitic N,N'di
with respect to the b axis in the ab plane of the crystal. Reprinted methyldiimide/anthracene EDA complex by Lesin et
from ref 261 with kind permission of R. E. Merrifield; copyright
1970 Elsevier Science Publishers B.V. al.276The additional maxima in this case are thought
to be due to level crossings of the '(TT), with 5(TT)2
and 5(TT)1pair states.
molecular crystals, with particular emphasis on an A MFD opposite to the delayed fluorescence is to be
thracene and tetracene. The reactive species of interest found for prompt fluorescence, the intensity of which
are singlet and triplet excitons and paramagnetic is decreased by the possibility of the reversible fission
(doublets) charge carriers such as electrons or holes (e, process
h+),which may be mobile or trapped (Drmob,D+mo,,,D, Si F! TT T + T
  
+
r 1
I 1 IS. I
01
I
1
90 60 30 ' 0 30 SD ' ' 90
OEGREES I I
Figure 11. The MFD of tetracene fluorescence as a function of
orientation of the magnetic field vector (4000 G) in the ab plane:
0 90
.. iao
9, orrantation
270 360
o f magnetic fis/d,[degi
(a) calculation of tripletpairstate energies; (b) experimental Figure 12. Anisotropy of photocurrent in an anthracenepyro
results, q ( H ) relative enhancement of fluorescence intensity. mellitic dianhydride crystal when the magnetic field is rotated
Reprinted from ref 259 with kind permission of N. Geacintov, in a fixed crystal plane for the field values indicated. The in
M. Pope, and F. Vogel; copyright 1969 American Institute of dividual curves are shifted relative to each other on the ordinate.
Physics. The scale of a 1%modulation of total current is indicated at the
top of the figure. Reprinted from ref 109 with kind permission
of N. Karl; copyright 1979 Elsevier Science Publishers B.V.
singlet and triplet excitons are produced by electron
hole recombination. The latter process, where a pair
of doublet states recombines, could also give rise to a
characteristic MFD according to the radical pair formation on the interacting species involved (TDR and
mechanism. In fact, Frankevich suggested this type of TTR; cf. Table 3). Ziegler and Karl" have used such
explanation for the dynamics of "weakly bound" CT measurements (cf. Figure 12) for a complete determi
states (Wannier excitons) where singlettriplet mul nation of the ZFS tensor of triplet excitons in crystals
tiplicity changes might occur according to the g mech of the anthracene/pyromellitic dianhydride EDA com
anism.231*274p284More recent evidence for involvement plex.
of the radical pair type mechanism with hfc as the In concluding this section, we note that there are also
singlettriplet mixing perturbation has been obtained a variety of MFEs in the field of luminescence and
by Klein et a1.254256from timeresolved luminescence, photoconductivity of inorganic solids and semiconduc
excited by highenergy radiation. The luminescence tors. Some of these are collected in the reviews by
intensity at 10050011s delay time displayed the typical Street40 and Cavenett117(cf. also section V1.G).
MFD of the hfc mechanism for geminate electronhole
pairs originating in an overall triplet state. This would
indicate that, in order to guarantee the overall singlet C. I n Homogeneous Liquid Solutions
spin state of the spur, a triplet exciton is also produced
l(eh+)* + So 
during thermalization of primary ejected electrons:
3(eh+)+ T1 (37)
By far most of the magnetic field effects on chemical
reactions have been found in liquid solutions, and most
of them are due to the radical pair mechanism. This
Other examples where the radical pair type mechanism results from a rather favorable relation of radical mo
is operating have been reported for solidliquid inter bility and solvent cage effect in liquids. Whereas in
faces and will be discussed in section 1V.E. gases separation of radical pairs is very fast and there
A great many MFEs have been revealed by photo is practically zero probability of geminate reencounters,
conductivity measurements in organic molecular crys in solid phases radical pairs are generally not capable
tals. These investigations have been pioneered by of separating efficiently unless one of the unpaired
Frankevich and coworkers (cf. Table 6). As first dem electrons can move as a conduction band electron or by
onstrated by Geacintov et the effects are pre electron hopping. In liquid phases cage reactions and
dominantly due to the detrapping of doublet charge diffusional separation of radical pairs may take place
carriers by interaction with triplet excitons: with rates of similar order of magnitude so that a MFE
T + 2D+t,
+ So + 2D+,ob (38) on the cage recombination may often lead to detectable
changes of product ratios. One should be aware, how
MFEs may be understood as a sequence of spinselec ever, that although the radical pair mechanism is really
tive interactions in the (TD) pairs determining the ef dominating in liquid solutions, magnetokinetic effects
ficiency of the charge carrier detrapping process. Of in such media can be also due to other pair mechanisms
course, the effect of TT annihilation will be also seen +
(T T = T + D) or to the triplet mechanism.
if this process contributes significantly to the decay of In the present section we deal separately with thermal
triplet excitons, thus determining their stationary con chemical reactions, photoreactions, and luminescence
centration, which will be reflected in the overall rate processes. Other effects in homogeneous liquid solution
of charge carrier detrapping. will be found in sections 1V.G (reactionyielddetected
The MFE on photocurrents, including its orienta magnetic resonance) and 1V.H (magnetic isotope ef
tional dependence, may be used to obtain detailed in fects).
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989,Vol. 89, No. 1 71
1. Thermal Reactions indicating that at lower fields the radical pair reactivity
is influenced by Ge hyperfine coupling, while a strong
Thermal reactions in liquid solutions have provided Ag effect predominates at higher fields. These results
the first examples of MFEs on chemical reaction yields seem to indicate the feasibility of magnetic isotope
caused by the radical pair me~hanism.',~Chemically, separation even for elements heavier than C and 0 (cf.
magneticfielddependent thermal reactions mainly fall section 1V.H).
into two classes: (i) reactions of alkalimetal alkyls with The MFE on the reaction between nbutyllithium
alkyl halides and (ii) decomposition of organic peroxides and ditertbutyl peroxide has been investigated by
and endoperoxides. Kurskii et al.132 Here the singlet radical pair l(n
The cases of the first type are listed in Table 7, with C4H9**OC(CH,),) is the primary geminate pair. The
some data characterizing their magnetic field depen decrease of cage product formation is mainly attributed
dence. The reactions, which seem to be the domain of to the Ag mechanism. A qualitative simulation of the
Russian workers, have been reviewed in some detail by somewhat oscillatory MFD could be achieved by taking
Molin et al.22*52 into account the influence of spin relaxation using a
The reagents are heated in nonpolar solvents such as
<1:
formalism developed by Kubarev et aL2" (cf. also sec
hexane or cyclohexane and react according to eq 39 tion V.C).
+
 Thermal decomposition of several endoperoxides has
7 escape BB. AB (39)
AM + BX MX + A* 8' been studied in magnetic fields by Turro and cowork
cepe e r ~ . These ~ ~ experiments
~ ~ ~have ~ been
 reviewed
~ ~ by
Formation of a singletspinaligned radical pair of a Gould et al.53 Thermolysis of the endoperoxides yields
benzyl and an alkyl radical is the primary reaction step. molecular oxygen originating to some extent as singlet
Cage recombination of the radical pair leads to the oxygen, which may be determined quantitatively by
unsymmetric coupling product AB, whereas escape trapping it in a reaction with tetracyclone (2).
yields the symmetric coupling products AA and BB, Ph Ph 0
and the unsymmetric one in statistical ratios. Spin
evolution in the primary singlet radical pair leads to
tripletspin alignment, which precludes recombination
and hence favors escape product formation. U
Soon after the discovery of CIDNP in such 2
3
MFEs were found to modify the ratio of cage to escape
products, characterized by the product ratio [AB] / Whereas the singlet oxygen yield with the 9,lO
[AA], which was determined by NMR analysis. The endoperoxide 4 shows a strongly negative MFD between
magnetic field dependence has not been measured in 1 and 1.4 T ( R = 6.2%, 15.6%, and 28% at re
full detail in every case but the data are qualitatively spectively 0.95, 1.15, and 1.35 T), the singlet oxygen
consistent with the hyperfine coupling mechanism yield in the case of the 1,4endoperoxide 5 is magnetic
modified in several cases by the Ag mechanism, which field independent. These findings correspond with
is indicated by a sign inversion of the effect between Ph Ph R
low field and high field.
Theoretical simulation of the M F E s ~is ~only possible
if extremely long cage times are assumed, which cannot
be understood on the basis of free diffusion of neutral
radicals. An explanation is offered in terms of associ Ph Ph R
ation of the radical pairs to lithium oligomers, known 4 5a, R = C H ~
to exist in such solutions. This situation is in some way b. R = OCH3
reminiscent of the large effects in micellar aggregates other mechanistic evidence141 indicating that the de
discussed below. composition occurs by a concerted mechanism for 5 and
It may be of special interest that Table 7 also contains by a diradical mechanism for 4. The MFE in this case
some examples with germanium compounds. Experi is attributed to the influence of the Ag mechanism,
ments have been performed with samples of natural favoring intersystem crossing in the singlet diradical
germanium isotope abundance, i.e., with about 7% of species. Also, 170magnetic isotope effects have been
',Ge, exhibiting a fairly strong hyperfine coupling con discovered,147which will be commented on below (cf.
stant of 24 mT. In fact, the MFE is of the case 1,2 type, section 1V.H).
72 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
TABLE 8 (Continued)
method of
reactantsa solventb observationc characteristics of MFEd ref
+
3DQ solvent glycerol + EtOH F P R(radica1 yield), case 2: R(125 mT) = +lo% Margulis et ale1%
+ solvent glycerol + EtOH FP R(radica1 yield), case 2: R(125 mT) +12% i
;:
3XOnXH (24n) ACN LFP T) = 2.8, 4.7, 7.9, 7.9, 16.9, 15.0, Tanimoto et al.362
r ~ p ( 0 . 8T)/TR~(O
19.1 (n = 2, 3, 4, 5, 6, 8, 12)
Homolytic Bond Cleavage
dibenzoyl peroxide toluene VPC R(yie1d of cage product), R ( l T) 4%, R(4 T) =
i
;: Tanimoto et al.I3O
(SI sens) 8% Ag RP mechanism
R(various product yields), case 2, case 1, 2 Sakaguchi et al.613322
3ditertbutyl ketone ndecane GLC R(cage product pivaldehyde), case 1: B I I z 10 mT,i
;: Fis~her~*~
R, 17% i
;:
3alicyclic ketones (26n) MeOH LFP R(biradica1 decay constant), case 1, 3: BM variable Zimmt et al.324
with n, RM = +13%, R, > 16%
Miscellaneous Reaction Types

transolefins. 3sens
trans cis isomer
CP. GLC R(isomerization rate), R(0.9 T) = 2 to 17%
Reactants: Ac, anthracene; An, aniline; AQ, anthraquinone; BP, benzophenone; BQ, benzoquinone; DQ, duroquinone; DABCO, diaza
bicyclo[2.2.2]octane; DEA, N,Ndiethylaniline; DMA, NJVdimethylaniline; DMT, N,Ndimethylptoluidine; DCNB, pdicyanobenzene;
DMAP, p(dimethy1amino)pyridine;DMDMA, 3,5dimethoxyN,Ndimethylaniline; FMN, flavine mononucleotide; Py, pyrene; TH+, thio
nine; TMPDA, N,N'dimethylaminophenylenediamine. Solvents: ACN, acetonitrile; cH, cyclohexane; DMF, N,Ndimethylformamide;
EtOH, ethanol; iAmOH, isoamyl alcohol; MeOH, methanol; PrOH, propanol. Methods: CP, continuous photolysis; DF, delayed fluores
cence; F, fluorescence; FP, flash photolysis; LFP, laser flash photolysis; PC, photoconductivity; PSFP, photolysis by sequence of flash light
pulses; TPLFP, twopulse laser flash photolysis; TSLEF, twostep laser excited fluorescence; GLC, gas/liquid chromatography; TLC,
thinlayer chromatography; VPC, vapor phase chromatography. Charcteristics: R ( X , a...), relative magnetic field effect on quantity X at
specified conditions a,..; case (...) used for phenomenological, not mechanistic classification of MFD (cf. Figure 6); af,quantum yield of
fluorescence; @trpnacis, photochemical transcis isomerization quantum yield; i, photocurrent.
ArN2' + 5Fe2+ t
5
ArN2' Fe3+  ArN2' + 6Fe3* (42)
I a0501 c5 CDdmj I
100 200 650 mol
magrrtic field. Gauss Figure 16. Bllz values of MFE on pyrene triplet formation in
fluorescence quenching by N,Ndimethylaniline in methanol.
Figure 15. MFD of pyrene triplet yield produced by fluorescence Dependence on donor concentration CD () Theoretical results
quenching of pyrene by Nfldimethylptoluidine in acetonitrile. according to ref 651; () Heisenberg energy broadening effect
The triplet yield was derived from delayed fluorescence mea corresponding to electron hopping between donor molecules.
surements. Reprinted from ref 306 with kind permission of A. Reprinted from ref 307 with kind permission of A. Weller;
Weller; copyright 1983 Elsevier Science Publishers B.V. copyright 1983 Elsevier Science Publishers B.V.
were performed by Frankevich's group. They were able ious aromatic amines, with some of their D or Fsub
to demonstrate that a sign inversion of the MFE on the stituted derivatives, or with dicyanobenzene:
yield of free ion radicals occurs when going from ace
tonitrile (DK = 38) to isopropyl alcohol (DK = 18).762 B l p = 2(B1' + B?)/(Bi + Bz) (43)
This effect, which was also observed in solvent mix The individual B, values characterizing the radicals (i
t u r e ~was
, ~ attributed
~~ to the occurrence of singlet = 1, 2) are given by
exciplex formation from the radical ion pair in the less
polar solvent, so that in this case the lifetime of the B, = (CI,,(&,+ l)a,2)1/2 (44)
singlet radical ion pair becomes shorter than that of its
triplet counterpart, whereas in acetonitrile, where the Equation 43 gives numerical results similar to those
singlet exciplex is less easily accessible, the opposite is from an expression derived by S ~ h u l t e n ~ ~ O
true. [1 1/3(&/B1/~)~1[1
 1/33(Bz/Bi/~)~I
= 0.9 (45)
The reversibility of fluorescent exciplex formation
from geminate radical pairs has been demonstrated from a semiclassical consideration of electron spin
more directly by MFEs on the exciplex fluorescence motion. From the agreement of experimental BlI2
quantum yield (cf. section 3). These effects may be values with eq 43 or 44 one may conclude that the
particularly pronounced if donor and acceptor radical lifetimes of the radical pairs investigated are longer than
are linked together by a mobile molecular chain. Since T = h/B,,z.
in such a case the magneticfieldindependent dissoci Experimentally, it was first shown by MichelBeyerle
ation channel is closed, the magnetic field dependence et al.312with the anthracene (Sl)/DMA system in ace
of the radical pair lifetime becomes most pronounced tonitrile that B1 increases as the delay time of the
(vide infra). The MFD of the triplet yields (MARY probing laser puke is decreased. Thus for delay times
spectra) in the numerous investigations by the groups of 15, 7, and 5 ns, BIlz values of 5.1, 5.8, and 6.9 mT
of Weller and MichelBeyerle is generally of case 1type. were observed, respectively.
The effects are governed by the magnetic field modu This effect has been reproduced t h e o r e t i ~ a l l y Its
.~~~
lation of the hyperfine coupling mechanism, since the obvious interpretation follows from inspecting a dia
range of magnetic fields was generally not extended gram showing the spin evolution of a radical pair in
above 0.1 T and the & mechanism is of no importance various magnetic fields (cf. Figure 46). MFEs are first
here. It has been found that the typical value of Bllz seen at longer times, and the crossover from the zero
(cf. Figure 15) depends in a characteristic way on the field curve to the limiting highfield curve occurs at
hyperfine coupling constants of the magnetic nuclei and successively shorter times as the magnetic field is in
on the lifetime of the radical pairs. It is, however, not creased. The analytical formula provided by Haber
always the chemical lifetime but rather the effective korn331for the shorttime behavior (cf. section V.C.3)
electron spin correlation time that is of importance. describes this feature quite nicely. The phenomenon
The latter may be shorter than the chemical lifetime may be also conceived as a lifetimebroadening effect.
in the case of electron hopping between radicals and Due to the short delay time of observation, the energy
diamagnetic molecules or in the case of earlytime levels are broadened and higher magnetic fields are
probing of the MFE, i.e., by the time delay in time necessary to provide a Zeeman splitting sufficient for
resolved measurements. Only if all of these lifetime separating the individual levels. Such lifetimebroad
determining processes (chemical, electron hopping, and ening effects have been also observed by Weller's
probing) are sufficiently slow (usually longer than 20
ns) is the B1p value indicative of the effective hyperfine Similar effects on Bllz are observed when the donor
coupling in the radical pair. This was demonstrated by concentration is increased, so that electron hopping
the occurrence of a H/D magnetic isotope effect on the between diamagnetic donor molecules and donor rad
A quantitative correlation was
B 112 va1ue.112~303*306~314 icals may occur during the lifetime of a geminate
established by Weller et al.306using a series of 16 dif pair.305.307,313,314
ferent combinations of pyrene or pyrenedlo with var In Figure 16 is shown the increase of the Bl12value
76 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
as the DMA concentration for pyrene singlet quenching reaction^.^^^^^^^ Geminate recombination requires trip
in methanol is increased. The straight line, describing letsinglet transitions in the radical pairs, which are
the initial slope of the BII2versus concentration of DMA sensitive to magnetic fields. Therefore the free radical
curve, corresponds to the lifetimebroadening effect; the yield, too, should exhibit MFEs. It should be noted,
deviation from this slope at higher DMA concentrations however, that if radical escape is the predominant
has to be explained by an exchange narrowing, which channel, its magnetic field modulation by the mag
comes into play if many hopping processes during the neticfielddependent recombination process is generally
radical pair lifetime wipe out the effect of the donor small. On the other hand, probing the yield of geminate
hyperfine coupling. In the limiting case, which has not recombination to the ground state is a more difficult
yet been approached experimentally, one should expect experimental task, since usually a large background of
that the B1,2 value is even lower than at low donor groundstate molecules not taking part in the photo
concentrations because then it is only determined by process is present. Thus, in order to create favorable
the hyperfine coupling in the acceptor radical. It has conditions for observing MFEs on the free radical yield,
also been noted that the effect of probing pulse delay the efficiency of the escape channel has to be decreased,
time on B l j zcan be suppressed if the lifetime broad which is usually done by lowering the temperature or
ening by the hopping process is strong enough.307 by using highly viscous solvents.
It is of interest to note that electronhopping effects The first effects of this type were observed by Per
between donor radicals are also demonstrated by unu iasamy and Linschitz315for the electrontransfer reac
sual CIDNP patterns obtained in the pyrene singlet/ tion between DABCO and fluorenone triplet in pro
diethylaniline system with high donor concentration^.^^^ pylene carbonate. Their results, which were obtained
A mechanism similar to that in the singlet radical ion over a wide temperature range, illustrate the arguments
pairs mentioned above, with a more efficient recom given above: whereas at 343 K and 1 CPwith a zero
bination into the triplet channel, has been invoked by field radical yield of 0.89 the maximum MFE was only
Tanimoto et al.172to account for the MFE shown by the 1.6%, at 223 K and 45.3 CPwith an absolute radical
photoconductivity of tetramethylpphenylenediamine yield of only 0.13 the MFE amounted to 24%. The
(TMPDA) photoionized by the action of 308nm laser MFE was saturated at fields above 27 mT and is of the
pulses. It was assumed that the e/TMPDA*+ pair case 1 type, indicating the influence of the hyperfine
produced on photoionization may dissociate to yield coupling mechanism.
free charges, detectable by photoconductivity, a process Highsolventviscosity and lowtemperature effects
that has to compete with singlet/triplet spin evolution have also been successfully applied by Kuzmin and
and successive pair recombination to yield the TMPDA ~ o  w o r k e r s to
~ ~observe
~ J ~ ~ MFEs on the radical yield
triplet state. Since triplet pairs are formed less effi from triplet electrontransfer reactions. Radicals pro
ciently in magnetic fields, this is favorable for the yield duced in a reaction between benzoquinone triplet and
of dissociated charge carriers. The fairly high B1/2value 2propanol were spintrapped and the adducts quan
of 0.13 T indicates that electron spin relaxation may titatively assessed by ESR spectroscopy. Radicals
significantly contribute to the radical pair multiplicity produced in the reaction between duroquinone triplet
change. and p(dimethy1amino)pyridine in glycerol/ethanol
The singlettriplet multiplicity change in radical ion mixtures have been detected by conventional flash
pairs produced by photoelectron transfer between photolysis. The latter system yields rather high MFEs
stilbenes and singlet excited pyrene has been used by of up to 80% that are of the case 2 MFD type. Hy
Leshina et al.310for indirect sensitization of stilbene perfine coupling and relaxation mechanism contribu
transcis isomerization via the triplet channel. Rather tions are invoked to account for this.
strong MFEs of about 30% have been observed, but MFEs on the free radical yield from triplet elec
the MFD shows significant differences when stilbene trontransfer reactions in lowviscosity methanolic so
and its perfluorinated analogue are compared. Whereas lutions at room temperature have been found by Steiner
the former saturates at about 20 mT, the corresponding and c o  w o r k e r ~for~ ~the
~ Jreaction
~ ~ ~ ~between
~ thionine
behavior of the perfluorinated compound extends to triplet (6s)and various monohalogen anilines. Laser
about 0.1 T and turns to a case 2 behavior (Ag mech
anism) at higher fields. Theoretically, the MFD curves
are well reproduced on the basis of the semiclassical
model of spin motion. Furthermore, CIDNP effects
H2N'
Q1yJNH2
have corroborated the mechanism.311 6X ( X = O , S )
In connection with sensitized cistrans isomerization flash photolysis and steadystate photokinetics yielded
of olefins, it should be mentioned that an early report quantitatively identical MFD curves for the production
by Gupta and H a m m ~ n on d ~MFEs
~ ~ in tripletbenzo of semireduced thionine radicals and the permanent
phenonesensitized stilbene isomerization has not been photobleaching quantum yield of the dye. As shown
confirmed by other g r o ~ p s . ~ ~ ~ p ~ ~ ~ in Figure 17 the radical yield is decreased by a magnetic
(b) ElectronTransfer Reactions with Excited field, the MFE being enhanced by heavyatom substi
Triplet States. When radical pairs are produced by tution of the electron donor. The MFD curves show
electrontransfer reactions with excited triplet states, saturation above 1 T, with B 1 / 2values typically on the
their energy is usually too low to repopulate the locally order of 0.2 T.
excited triplet state. Thus the only possibility for re A first explanation of these effects was suggested in
combination is to the singlet ground state. Since this terms of the radical pair Ag mechanism.316 However,
process is spin forbidden for a triplet radical pair, the an application of more quantitative criteria, as follow
escape reaction usually dominates, so that free radical from a theoretical calculation by Schulten and Epstein@
yields are generally high in triplet electrontransfer on the Ag mechanism in triplet radical pairs without
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 77
3 :XI, +
(e.g., T D energy transfer) might be responsible for
the effects observed.
The MFD of various photochemical hydrogenatom
abstractions was studied by Margulis et al.156 These
authors used solvent mixtures of water or ethanol with
glycerol to obtain very highly viscous solvents. Varying
the temperature and the solvent composition, they
showed that the MFEs are determined by the value of
T/q.MFEs on the free radical yield (determined by
flash spectroscopy) or on the permanent bleaching re
action (determined by continuous photolysis) became
I
1 5 13 1; 23
detectable only at T / q values smaller than 10 K/cP. At
nognetic f L e l d [rGaussl room temperature this corresponds to viscosities larger
Figure 17. Relative MFE ( R ) on radical yield from triplet
than 20 cP. In the systems investigated by Margulis
quenching of thionine by halogen anilines in methanol: ( 0 ) et (cf. Table 8). The magnetic field causes an
piodoaniline; (m) oiodoaniline; (e) miodoaniline; (0)p increase of free radical yield, which results from a
bromoaniline. values given are absolute quantum yields of suppression of tripletsinglet transitions by a magnetic
radical formation in zero field. The solid lines are theoretical fits field. The MFD curves are of the case 2 type, which
according to the triplet mechanism (adapted from ref 160).
is taken as evidence for a contribution of the relaxation
mechanism. Remarkably, Margulis et al. also found
Coulombic attraction, the effects shown in Figure 17 are MFEs on the secondorder recombination rate constant
much larger and saturate at much lower fields than are in the case of riboflavin semiquinone radicals and
expected for the Ag mechanism. A quantitative inter benzophenone ketyl radicals. The secondorder bulk
pretation was then developed in terms of the triplet recombination rate is slowed down by the magnetic
me~hanism,~ which
~ 1 ~ comes
~ ~ into play through the field, demonstrating that F pairs behave rather like
intermediacy of a triplet exciplex formed as a primary geminate triplet pairs, which has also been confirmed
product in the electrontransfer reaction.336 in many CIDNP investigations.
It was shown that in a sandwichtype exciplex be MFEs in the photochemistry of quinoline and iso
tween electron donor and electron acceptor spinorbit quinoline derivatives have been reported by Hata et
coupling at the donorlocalized heavyatom substituent al.318320Photochemical hydrogen abstractions by the
will be much less efficient in that particular triplet ring nitrogen from the solvent ethanol are believed to
substate where the electron spin is oriented parallel to be the primary reactions in the photoreactions of 1
the aromatic plane of the donor.80 Thus the require isoquinolinecarbonitrile (7) and 4methylquinoline2
ments for the triplet mechanism, as described in section carbonitrile (9). For the reaction of 7 (eq 46) the
11, are met. From a quantitative analysis of the MFD
curves decay rate constants of several triplet exciplexes
could be determined. Thus, e.g., for the thioninelp
iodoaniline triplet exciplex rate constants of 6.8 X lolo
and 5 X lo9 sl were obtained for ISC (T So) and
radical formation, respectively.
 I
CN
15
13
16 (CH3)3CC(CH3)3 f co
solvents. The B, value depends on the type of alcohol
(49)
used. It moves to higher fields as the pK, of the alcohol
decreases (cf. Figure 18). The effects are suggested to
be due to the levelcrossing mechanism in a singlet photolysis of ditertbutyl ketone (16). The special
radical pair of structure 14, which is assumed to mediate attraction of this reaction as an example of a magnet
icfielddependent reaction lies in the fact that in the
tertbutyl radical there are nine magnetically equivalent
protons so that an exact expression for the spin motion
in general fields may be easily obtained (cf. section V).
The MFE is slightly positive at low fields, which is
characteristic of the onecouplingconstant spin system,
1 14
and is negative at higher fields with a saturation be
havior characteristic of the hyperfine coupling mecha
nism. The theoretical results based on this mechanism
an excitedstate proton transfer, furthering formation reproduce the experimental data quite well, although
of the lactam isomerization product. A singlet/triplet it is essential to use a correct relaxation rate constant
transition in 14 would favor radical pair dissociation, for the pivaloyl radical. This parameter had been de
which is thought to lead finally to preferential regen termined in previous ESR experiments.
eration of the starting material. The mechanism must Whereas with one exception related to the triplet
certainly be regarded as rather speculative. The find mechanism, all MFEs in liquid solution reviewed in this
ings borne out in Figure 18 are, however, unique in the section are manifestations of the radical pair mecha
field of photochemical MFEs in that they represent the nism, recent studies by Ferraudi and c o  w o r k e r ~ ~ ~ ~ , ~ ~ ~ , "
only examples of apparently pure case 3 MFD curves, have contributed novel mechanistic aspects to photo
corresponding to fairly sharp T/S level crossing reso chemically relevant processes in liquid solutions. Ap
nances. In contrast, the biradical results reviewed below plying magnetic field pulses up to 2.4 T, they found
(section e) are characteristic examples of cases with a marked effects on the quantum yields of the photo
dynamical distribution of S/T energy gaps. aquation of [Rh(NH3),X] (X = C1, Br) and of K2[Co
(d) Homolytic Bond Cleavage and Other Types (CN),] (cf. Table 8). In the latter case the ratio k~!k,
of Reactions. Photochemical decomposition of di of the rate constants of photoreaction (kR)and radla
benzoyl peroxide (15) is one of the early examples of tionless decay (k,) increased by a factor of 3 when a
a photochemical MFE in liquid solutions. It was re magnetic field of 2.4 T was applied. The explanation
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 79
LF:;:
Jqy...
IO ..
. . . . . . .’i.
chain
length
nS6
energy
relations
molecular triplet
formation
2Je, > 2Jmh > AEM none from radical pair
\ ..... . . . . . . . .”..
n 1 12
*T(B 
6 < n < 12 2Jen > AEm > Zr,, OT(BM)> OT(B = 0) >
m,
AEM > We, > 2Jmb as in unlinked systems
*..
. . . . . . . . . . . .
10
. . .....
.... orbital states in a 1(3E, + 3&) encounter pair, which are
Ol:_;.; . . . .. ... . . . . . . 9 assumed to exhibit largely different activation energies
...... ....... . . . . “. ‘8 6 . ’ .  for excimer formation. The MFE is assumed to come
................................ L L in through a magnetic splitting of the four 1(3E, + 3E,)
ob 500 1000 1500 5000
states. These would correspond to the (i] manifold in
Magnetic Field Strength B i Gauss
terms of the general mechanistic view developed in
Figure 19. Triplet absorbance observed as a function of magnetic section 11.
field strength in linked EDA systems pyrene(CH,)DMA (18n) (e) Biradicals. In some of the systems listed in
in acetonitrile. Reprinted from ref 309 with kind permission of
A. Weller; copyright 1986 SpringerVerlag. Table 8, the radical pairs originating from the respective
photochemical primary reactions are linked by a poly
methylene chain. There has been considerable interest
h l
I /
/ T +l in the dynamical and spin properties of such biradical
and the study of MFEs on the decay of
such species is expected to be particularly instructive
as far as spin exchange interaction, intersystem crossing
mechanisms, and the dynamics of the chain endtoend
distances are concerned.
AE
hlc I SO Weller and ~ ~  ~ ~ r investigated k e r the
pyrene/dimethylaniline pair linked by a polymethylene
s ~ ~ ~
chain of n = 612 (1811).As for the separate donor/
T1
I I
c
24 n
+ + 25n
!side product1
radical positions are well defined. For n = 212 the
biradical decay has been directly observed by laser flash
Figure 21. Reaction scheme for magneticfielddependent spectroscopy. In zero field the decay times (0.10.22
photolysis of linked electron donoracceptor systems 2011(after p s for n > 2,0.98 p s for n = 2) are longer than expected
Nakagaki et aL317). for the ISC process on the basis of the hfc mechanism.
However, very large MFEs on the decay times ensue,
interpreted without accounting for the dynamics of the even for n = 2 (cf. Table 8). These effects increase with
endtoend distance (cf. also below and section V). n, leveling off at n = 12, where the lifetime is increased
Another singlet biradical system originating from by a factor of 20 in a field of 0.8 T as compared to zero
photoelectron transfer in the linked compound 1911was field. The MFD of 7 increases monotonously and is not
investigated by Tanimoto et al.,351 observing the emitted saturated at 0.8 T. Spinorbit coupling, as invoked to
exciplex fluorescence intensity. For comments on this explain the decay rates of some acylalkyl biradicals
system, cf. section 3. (vide infra), does not seem to be of importance here.
A biradical system generated in the triplet spin state The effects are attributed to a combination of the hfc
by intramolecular electron transfer was investigated by and the relaxation mechanism.
Nakagaki et al.317(cf. Figure 21). The reaction was Biradicals with varying endtoend distances may be
followed by stationary photokinetics. The quantum conveniently produced by using Norrish type I cleavage
yield of disapeparance of the starting material decreases reactions of alicyclic ketones. Magnetic interaction in
in a magnetic field, which indicates an initial triplet biradicals from such reactions was first studied by Closs
multiplicity of the radical pairs. MFEs are observed and Doubleday3*l in 1973, using the CIDNP method.
only for n I8. Again, this points to the distance de A number of further investigations of this type have
pendence of the exchange interaction, which is pro been reported It was found that the CIDNP
hibitive for magneticfieldsensitive intersystem crossing intensity passes through a maximum at a field strength
processes at short endtoend distances. B,, increasing with decreasing chain length.
Examples of photochemical MFEs due to triplet bi While this behavior reflects the general distance de
radical intermediates that are produced by intramo pendence of exchange interaction between biradical
lecular Hatom transfer have been reported by Tani termini, it was learned from a detailed theoretical
mot0 et a1.327J52 analysis of the MFD of CIDNP intensity by de Kanter
The anthraquinone derivative 22 undergoes photo et aLM (cf. also section V) that the positions and widths
reductive bleaching,327whereby, among other products of the CIDNP maxima do not simply reflect the qua
involving reaction with molecular oxygen present in the sistationary distribution of exchange interaction, as
solution, a cyclic ether 23 is formed as an intramolecular would be expected from the endtoend distance dis
coupling product from the biradical. The H abstraction tribution, but depend critically also on the chain dy
H&(CH2)13n namics. This point has also been confirmed in a recent
\ theoretical study by Schulten and c o  w o r k e r ~ . ~ ~ ~
~cH,), It has also been concluded from CIDNP experiments
0 ’ ‘ 0 that tripletsinglet transitions in biradicals of medium
and short chain length are largely due to the spinorbit
coupling mechanism, which is not sensitive to a mag
netic field, and most efficient in diradical conformations
I with close endtoend approach. Therefore CIDNP
OH
intensities strongly decrease with decreasing chain
22 23 length.
is probably not very selective for the H position in the Recently, Closs et aLM applied timeresolved CIDNP
terminal part of the C14 chain. However, occurrence of to probe biradical decay. The growin times of nuclear
a MFE R I 12% with B1 i= 15 mT for the bleaching polarization for cyclic coupling and acyclic dispropor
yield indicates that there should be major contributions tionation products from 1.6 and 1.8 biradicals were
from CH positions that may separate far enough from found to be of the order of 100 ns.
the semiquinone radical spin in the extendedchain The first direct timeresolved detection of alkylacyl
conformation. biradicals was reported by Turro and coworkers3z4~~g~3~
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 81
1.5 0 0
16
11
II ? I
12
11
H2N 0 H2N 0
12 10
28 (LH2) 29 (LO2) 30 (AP2)
1.o
0 9J,
0
e: 200 LOO 600 800
I
1000
Magnetic Field Strength BiGauss
The chemiluminescence induced by oxidation of lu
minol with potassium ferricyanide showed a very weak
MFE (Rs = +0.16%, B112= 3 mT, Bs 6 mT), that
required very sophisticated experimental equipment (cf.
section 111) in order to be reliably d e t e ~ t e d . ” ~The
chemiluminescence is thought to be due to the following
Figure 23. MFD of the relative exciplex fluorescence intensity
Q’ = Z’(B)/Z’(O) of compounds 18n (n = 816) in acetonitrile.
reaction steps:
LH2 + 20H  L2 + 2H20 (52)
Reprinted from ref 98 with kind permission of A. Weller; copyright
1985 Elsevier Science Publishers B.V. L2 + Fe(CN)t  L o  + Fe(CN)64 (53)
very small (about 1%) because the lifetime of the gem 2L* + 0 2 L022 +L (54)

b
Ti + So
by van Willigen364for pyrene. According to a detailed doublet spin are concentrated on fewer pair eigenstates
theoretical analysis by Lendi et al.,69 it should be ex than in zero field so that, according to the Merrifield
plained as a consequence of the triplet pairs' singlet model, a magnetic field reduces the average rate con
quintet energy splitting. It is a levelcrossing effect, stant of such processes.
which is, however, borne out only under conditions Effects of this kind have been reported by Faulkner
where the triplet pair lifetime is fairly long (for details, and Bard368for the delayed fluorescence of anthracene
cf. section V). in the presence of Wurster's blue cations (TMPDA'+).
Another case of triplettriplet interaction, particularly At a radical concentration where the quenching process
important in photochemistry, is encountered in the (58) determines the lifetime of the triplets, a monotonic
quenching of excited triplets by molecular oxygen. increase of delayed fluorescence is observed, which is
Experiments by Tachikawa and Bards5 on the delayed explained by the impeding effect of the magnetic field
fluorescence of anthracene and pyrene exhibited a sign on the triplet + doublet quenching process, leading to
inversion of the MFE from negative at low oxygen a higher stationary triplet concentration and hence to
concentrations to positive at higher oxygen concentra a higher delayed fluorescence intensity (R(0.8 T) =
tions. This could be an indication of the impeding +2%). The change from a (T + T)type MFD of de
effect of a magnetic field on the reaction layed fluorescence intensity to a (T + D)type behavior
3T + 302 '13v5(T0,) So + ' 0 2 + (57) has been demonstrated with variable concentration of
radical quenchers (TMPDA'+, benzoquinone anion
which would account for the observation, if quenching radical) by Tachikawa and Bard.369
by oxygen determines the triplet lifetime. The effect The simultaneous presence of excited triplets and
is only seen in DMF but not in acetonitrile. high concentrations of radical ions is a typical situation
The problem of how the rate of triplet quenching by in electrogenerated luminescence, where radical ions
oxygen should depend on a magnetic field has been produced in electrode processes recombine to produce
theoretically investigated by Stone and Swenberg366 and excited states. A classification of ECL systems may be
by Geacintov and S ~ e n b e r gwho , ~ ~pointed out that CT based on the criterion whether the ion recombination
interactions in the (T 302) pair might cause rahter large energy is sufficient to produce excited singlet states (S
singletquintet level splittings, which might prohibit route) or only triplet states (T route). As has been
any transition between them so that no magnetic field shown by Bard and c o  ~ o r k e r s , MFEs
~ ~ ~ may
~ ~ ~be
effects are to be expected. In fact, Swenberg and used to distinguish between these routes (for reviews
G e a ~ i n t o v failed
~ ~ ' to see magnetic field effects on ox of this work, cf. Atkins and Lambert,17 Faulkner,21
ygen quenching when investigating the delayed Sagdeev et a1.,22and Salikhov et al.52). Only energy
fluorescence of polynuclear aromatics adsorbed on deficient systems, i.e., those following the T route,
polystyrene. showed MFD of ECL. In these cases positive MFEs up
(c) TripletDoublet Pairs. The rate constants of to +30% (rubrene ECL from rubrene anion radical and
(T + D)pair reactions (usually triplet quenching by TMPDA'+)3" have been observed (cf. Figure 24), which
radicals) leading to a (S + D) pair of products (eq 58) are attributed to the (T+ D)mechanism. For Sroute
depend on the distribution of doublet character over systems MFEs according to the radical pair mechanism
84 Chemical Reviews, 1989, Vol. 89, No. 1 Seiner and Ulrich
might be expected. Such effects have, however, not Yet the radical pair thus produced is within the Onsager
been reported under ECL conditions. escape distance of about 30 nm, and charge recombi
In ECL systems that are not too strongly energy nation will be mostly geminate. Since in nonpolar
deficient (e.g., rubrene cation + anion)361changes of solvents the recombination energy of ion pairs is very
solventZ6lor supporting electrolyte concentration370may high, reaction 62 is diffusion controlled. Furthermore,
cause a shift from the T route to the S route, which is the multiplicity of the excited state M* is not subject
borne out in a decrease of the MFE. to energy restrictions but depends only on the spin
Magnetic field effects in ECL have also been reported correlation of the radical pair prior to recombination.
by Santanham and c o  ~ o r k e r s . In
~ ~ECL
~  ~systems
~~ The total electron spin of a spur is singlet.389 If, how
involving riboflavin anion with rubrene cation, the re ever, more than one pair is in a spur, various combi
combination fluorescence from rubrene exhibited a nations of individual radical pairs from it may have also
marked MFE (RDF(0.4T) = +28.6%), taken as evidence initial triplet spin correlation. The problem of calcu
that the luminescence is generated via the T lating the S/T ratio of possible pairs within such spurs
There are also exceptions to the “energy deficiency has been a matter of some debate,392395 which does not
rule” for magnetic field effects in ECL. Periasamy et seem to be completely settled. Nevertheless, it is clear
a1.375observed a large MFE (R(1 T) = +300%) in the that, as the spur size increases, the T/S ratio will ap
ECL generated via phenanthrene cation/anion radical proach the statistical limit of 3. For actual situations,
recombination, although in this system the ion recom however, the T/S ratio is smaller than 3 and the re
bination energy exceeds the phenanthrene SI energy by combining pair will show spin correlation effects typical
0.6 eV. As an explanation it was pointed out that even of initial singlet radical pairs.396
if the recombination energy is sufficient to populate the The recombination rate of singlet radical pairs is
S1 state, formation of triplets is not excluded. Fur directly reflected in the intensity of radioluminescence
thermore, phenanthrene shows very efficient intramo emitted. The suggestion that an effect of initial spin
lecular triplet formation (aIsc= 0.81, allowing for a correlation and successive spin evolution, which might
considerable contribution of emission in a subsequent be modified by external magnetic fields, should be de
triplettriplet annihilation process. tectable in the radioluminescence was first advanced
A very particular situation has been investigated by by B r o c k l e h u r ~ t .It~ ~
is~of interest to note that this
Razi Naqvi et al.,374who studied tripletdoublet energy suggestion was made a t the same time, but independ
transfer from triplet benzophenone to benzophenone ently of the suggestions of the radical pair mechanism
ketyl radicals. Since fluorescence intensity from the invoked to explain the CIDNP effects. Whereas
benzophenone ketyl radicals could be observed, this Brocklehurst first thought that spin evolution and its
provided a direct measure of the efficiency of the T + magnetic field dependence should be described in terms
D process. The emission intensity is increased by 1% of spin relaxation, some years later he established the
in a field of about 100 mT and is decreased to values relation with the CIDNPtype spin motion, showing
lower than at zero field a t about 300 mT. Whereas the that a coherent process driven by isotropic hyperfine
decreasing part is in accord with what is expected from coupling was essentially responsible for the observed
simple theories of tripletdoublet interaction, no defi effects.391
nite mechanistic interpretation was offered for the in Spin correlation and magnetic field effects have been
itial rise of the MFD. dealt with in several review papers.33i46,52,56v761 Never
theless, we think it useful to document the state of
4. Radioluminescence investigations in this field by a comprehensive list of
systems studied (cf. Table 10) together with some brief
When highenergy radiation (X and yrays, fast CY comments on various aspects of the work. We have not
and ,&particles) is absorbed in condensed matter, a included here investigations applying magnetic reso
number of ionization events occur along the track of the nance methods (RYDMR) since these will be covered
incident particles whereby cation and anion radicals of in section 1V.G.
suitable solutes may be finally formed, which on re To investigate MFEs radioluminescence has been
combination give rise to scintillation pulses or steady observed by stationary methods (when excited by y
state radioluminescence.33~46~56~389~390At high solute radiation or a @source)or by timeresolved fluorescence
concentrations the main reactions following the primary measurements when excited with e pulses from elec

reaction (59) are391(S = solvent, M = solute)
S S+ + e (59)
tron accelerators. Time profiles of scintillations have
been measured by the singlephotoncounting techni
que.
The first MFE in radioluminescence was reported
S+ + M + S + M+ (60) with pulse radiolysis for fluorene as emitting species in
squalane, a highly viscous aliphatic ~ o l v e n t . In ~~?~~~
timeresolved measurements it was shown that the
fluorescence intensity increased by about 40% in a
M+ + M +M* + M (62) magnetic field of 0.3 T and the triplet recombination
If the energy deposited in reaction 59 is high, the sec yield, detected by transient absorption, increased by
ondary electron may cause further ionizations so that 10%.
the spur comprises more than one ion pair. In general, Fluorene was also investigated in cyclohexane and in
the spur size depends on the energy and charge of the benzene, observing steadystate fluorescence under
primary particles and the type of solvent.390In alkanes y  i r r a d i a t i ~ n The
. ~ ~ ~MFE is largest with squalane and
the secondary electron from reaction 59 will travel a zero with benzene. In the latter solvent no radical ions
typical distance of about 7 nm before it is scavenged. of the solute are produced. The energy is directly
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 85
transferred to fluorene from excited states of the sol MFE is largest with vacuumUV radiation and smallest
vent. with aparticles. These results indicate that nonge
Other steadystate fluorescence investigations were minate ion recombination contributes more to the total
performed with naphthalene and its deuteriated or radioluminescence if high ion concentrations are pro
perfluorinated and also with biphenyl duced with multipair spurs and possible overlap of
and its perfluorinated derivative.381 These investiga successive spurs in a track as to be expected for air
tions have shown that the larger the hyperfine coupling radiation.
(F > H > D), the larger is the B,,, value. Since spin evolution due to isotropic hyperfine cou
Radioluminescence of perfluorinated benzene in pling is a coherent process, oscillations should appear
hexane, which has been investigated by Molin's in the singlet probability of a geminate radical pair, and
group,382is of special interest in that only nuclei with hence in the radioluminescence intensity, if there are
equal and rather strong hfc constant govern the spin only a few different coupling constants or if they occur
evolution. For this case theory predicts a MFD that in simple multiple ratios. Such a phenomenon is be
passes through a minimum a t low fields before it lieved to show up in the radioluminescence of 2bPPD
changes spin and saturates with a positive MFE at high (31)solutions (cf. Figure 25) investigated by Klein and
fields.52 These features are clearly borne out by the Voltz.169,387,388
experimental results.
Timeresolved measurements with the singlepho
toncounting technique have revealed that the time
necessary to develop a magnetic field effect on radio
91 (PbPPD) 32 (PPO)
luminescence is typically some 10100 ns, whereby the
growingin time of the MFE depends on the strength Quantum beats, which have been directly related to
of the hyperfine coupling as first demonstrated by the hfc constants of the respective radical pairs, have
B r o c k l e h ~ r s t 'for
~~~pterphenyl
~~~ and its per been observed by Anisimov et al.1671386
using twosolute
deuteriated derivative. systems with perdeuteriated pterphenyl as the cationic
A comparative study of MFEs with different kinds species and tetramethylethylene or durene as the an
of highenergy radiation was reported by Klein.169 The ionic species. The quantum beats are clearly resolved,
86 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
Primary Dhotoorocesses
iZe
or
Jc,
* PB.]
*2B t
mic
%cape products
e g A  A 85 4  3
D. I n Micellar Solution
1. General Situation and Methods
TABLE 11. Magnetic Field Effects on Radical Pairs from aCleavage of Ketoqes in Micellar Solution
ketone" surfactant* type of exptC ref
DBK (33) HDTC 13C enrichment Turro et ~.143,402,4C4*,413
CP. caee effect Turro et al.l19
SDS LFP, Gnetics Hayashi et a1.,161
Sakaguchi et al.1629424
HDTC LFP, kinetics Sakaguchi et al.,424
Turro et al.4119412
SDS, HDTC CP, 170enrichment Turro et al.la
SDS LFP, timeresolved CIDNP Turro et a11'.6
emulsion polymerization Turro et a1.142*414841s
SOS, SDeS, SDE CP, Bo dependent 13C CIDNP Zimmt et al?17
33a HDTC CP, cage effect Turro et al.1193401
TABLE 12. Magnetic Field Effects on Radical Pairs from HAtom Abstractions i n Micellar Solutions
H acceptor" H donorb surfactant' type of exptd ref
benzophenone (41) S SDS LFP, kinetics Sakaguchi et a1.4223423
CP, quantum yield Scaiano et al?43
CP, quantum yield of DPBF photooxidation Tanimoto et al.lM
SDS, HDTC LFP, kinetics Sakaguchi et al.,162v424
Scaiano et aLU3
CIDEP phase anomaly Murai et al.:31
Sakaguchi et aLrZQ
explanation by 3RP ESR Closs et
Buckley et aLU
52 SDS electron spin echo Thurnauer and MeiselU7
S, 52 CTAC LFP, yield of radical escape Scaiano et a1.442t443
52 DODAC vesicles CP (MF from Fe304particles), LFP Fendler,U8 Herve et al.l14
(yield of radical escape)
41 (did, 41 (13C) S SDS, CTAC LFP, kinetics Sakaguchi et a1.4238424
4 1ce S, 52 SDS, DTAC LFP, yield of radical escape Scaiano and LougnotM
naphthoquinone (42) S SDS timeresolved CIDEP Sakaguchi et al.429
LFP, kinetics Sakaguchi and H a y a ~ h i ~ ~ ~
LFP, MFE quenching by Ln3+ ions Sakaguchi and H a y a ~ h i " ~ ~
42a S SDS LFP, kinetics Sakaguchi and H a y a ~ h i ~ ~ ~
acetophenone (43a) S, 53 SDS LFP, yield of radical escape Hayashi et al.426
CTAB LFP,' kinetics Grant et allz1
butyrophenones
43b 56af SDS, CTAC, LFP, kinetics Evans et al.768
CTAB, Brij 35
43c 56c SDS
xanthone (44) 53 SDS LFP, yield of radical escape Hayashi et al.426
S SDS CP, quantum yield Tanimoto et a1.436,436
54 SDS LFP, kinetics
55 SDS CP, quantum yield; LFP, kinetics Tanimoto et al.136
53, 53 ( d ) SDS CIDEP, phase anomaly Sakaeuchi et al.430
carbenes 45, 46 52 SDSO/W LFP, &id of radical escape Scaiago and Lougnot164
microemulsion
anthraquinone (47) S SDS TSLE, rise of escape product Tanimoto et
47, 47a,b LFP, kinetics Tanimoto et a1.433
CP, quantum yield of bleaching Tanimoto et al.151
p  benzoquinones
48a S SDS LFP, kinetics Tanimoto and Itoh432
48ac S SDS CP, quantum yield of bleaching; LFP, kinetics Tanimoto et al.14Q
48e 56, 57f SDS LFP, kinetics Levin and Kuz'minUs
41, 42, 48ac,f, S, 54, 55 SDS CP, LFP, TSLE Tanimoto et a1.437
4951, 51a
Cf. Chart 2. bCf. Chart 3; S, surfactant as Hdonor. CTAC (=HDTC), cetyltrimethylammonium chloride; DODAC, dioctadecyldi
methylammonium chloride; DTAC, dodecyltrimethylammonium chloride; HDTC (=CTAC), hexadecyltrimethylammonium chloride; SDS,
sodium dodecyl sulfate. CP, continuous photolysis; DBPF, 1,3diphenylisobenzofuran;LFP, laser flash photolysis; TSLE, twostep laser
excitation. e Magnetic difference signal detection; cf. section 111. f Probably electron transfer followed by protonation.
TABLE 13. Magnetic Field Effects on Radical Pairs from Photoelectron Transfer i n Micellar Systems
acceptor donor" surfactantb type
.. of exptc ref
duroquinone (T,) (4812) diphenylamine SDS LFP, yield of radical escape Tanimoto et a1.434
acetophenone (T,) (43) diphenylamine SDS LFP, kinetics Tanimoto et al.43s
2,5diphenylbenzoquinone 4phenylaniline SDS LFP; kinetics Levin and K ~ z ' m i n , ~ ~
(TI)(48h) Levin et al.450
thionine (T,) (6s) aniline CDBAIbenzene LFP, yield of radical escape Schlenker et a1.43Q
CP, bleaching quantum yield Schlenker and S t e i n ~ ? r ' ~ ~
CDBA w/o, var cH20 LFP, kinetics Ulrich and SteineP3
halogenanilines, DMA CDBAIbenzene ( P E ) ~ LFP, kinetics Ulrich et aLUO
oxonine (S,)(60) TMPDA AOT/isooctane LE)^ LFP, kinetics Baumann et aLU1
pyrene (S,) DMA SDS LFPd (RYDMR), kinetics Grant et a1.lz1
DMA, N,Ndimethylaniline; TMPDA, N,N'tetramethylpphenylenediamine. * AOT, sodium bis(2ethylhexyl)sulfosuccinate; CDBA,
cetyldimethylbenzylammonium chloride; SDS, sodium dodecyl sulfate; *E, waterinoil microemulsion. LFP, laser flash photolysis; CP,
continuous photolysis. Magnetic difference signal detection; cf. section 111.
+ ked3.An explanation of its magnetic field dependence However, whereas in most work published before 1984
is provided by the magnetic field dependence of k,,,, it was generally assumed that the multiplicity change
which should be conceived as resulting from a spin is rate determining (i.e., kIsc = k,,,) even in zero field,
substateresolved kinetic scheme427,440 (cf. Figure 30). Hayashi and and Steiner and co
Here the actual recombination step is preceded by in w o r k e r ~have
~ ~pointed
~ , ~ ~out~ that in most cases this
tersystem crossing from the triplet to the singlet pair would not be in accord with the absolute value of the
spin state. The Zeeman splitting of the triplet levels hyperfine coupling (typically below 5 mT) and the
more and more suppresses spin transitions from the values of the MFD observed (typically on the order of
outer triplet levels, thus reducing the ISC efficiency and 1030 mT). Actually, in zero field the radical spin state
with it the overall rate constant of recombination. may be close to spin equilibrium, and factors other than
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 89
D * ] mic  I
kT  kaSc 2 CHART 1. Ketones Investigated That Undergo aCleavage
[ ’A + DHImic [ 3AH. + AH.+
2
D.)esc/m1c
I
II A + DH
krec
Imic
x aC
33 x
P
H ~ C  C H ~ ~ Y
H
35 x
X X Y x A X
Figure 29. Kinetic scheme for analyzing experimental decay
curves of triplet radical pairs in micellar solutions.  H H  H H
a CH3 H a CH3 H
T+IRPI b CH3 CH1 b H CH
c tBu tBu
d F H
e C1 H
f Br H
A’ 8’
34x
X A A’ B 8’ X A A ’ X Y
a H H H  H H H H
CH 3
zero field high field b H CH3 H a CH3 CH3 H H
CH 3
bd6 H CD3 H ad3 CH3 CD3 H H
Figure 30. Reaction scheme describing the kinetic relations CD3
bdg D CD3 D ad CD3 CD3 H H
between spin substates of the radical pair (RP) and the unreacted CD3
C CH3 H H
pair (UP) formed upon recombination. The short dashed arrows CH3 b CH3 CH3 CH3 tBu
d
indicate the reaction channel of micellar escape, which is equally CH 3 CH, CH3 CH3 c H P h H H
e
available for all spin substates. On the lefthand side is shown Ph li Ph H
the energy level scheme for the triplet substates in zero magnetic ed Ph D Ph D
field and in high field. E m denotes an average hyperfine coupling
energy; EZis the Zeeman energy (from Ulrich, Schlenker, and
SteinerMo).
? ?
C H ~  C  C H ~ X
U
spin ones, e.g., diffusion, may limit the rate constant 37x 3 9 ~ a,p 
of recombination. X A X X A B
It should be briefly mentioned that magnetic reso  H H  H 11
nance techniques have also revealed some interesting a H C H ~ a H C H ~
features specific to radical pairs caged in micelles. In b CH3 H b CH3 H
vestigating the MFD of 13CCIDNPintensities during
photolysis of DBK derivatives in micelles, Zimmt et
al.417found that it passes through a maximum at fields
between 27.5 mT (in SDS micelles) and 36.5 mT (in 0
SOS micelles). This behavior is similar to that of co 38x 40
valently linked biradicals and demonstrates the influ X A X
E I T L R N P L F I E L D STRENGTH Igoutsl
a
Ph Ph
(b)
pair formed with triplet spin correlation by the photo
reaction of the carbonyl triplet comprises a benzyl and
a phenylacetyl radical. After a fast change of mul
tiplicity, these may recombine to the starting material
or to the isomeric compound lphenylpmethylaceto
phenone (PMAP). However, by decarbonylation of the 1 1 L . I L
200 400 600 800
phenylacetyl radical, the primary radical pair may also E X T E R N P L FIELD STRENGTH Igourrl
undergo irreversible transformation to a secondary pair. Figure 32. Plot of MFD of rate constant ( k o b d ) of radical pair
Depending on the stability of the secondary radical thus decay in HDTC micellar solution: (a) ketone 3443; (b) ketone 34b.
produced, decarbonylation takes place with rate con Reprinted from ref 419 with kind permission of N. J. Turro,
stants between 6.4 X lo6 sl (PhCH2CO) and 1.3 X los Columbia University, New York; copyright 1985 American
sl ((Ph)2CHC0).421 Elimination of CO does not destroy Chemical Society.
the spin correlation. The correlated pair of two benzyl
radicals present after fast decarbonylation may undergo Recently, the magnetokinetic effect of H/D magnetic
intramicellar recombination, too, or else may separate isotope substitution in ketone 34 (cf. Table 11) was
by radical escape from the micelle. The extramicellar studied by Turro et al.767 There is a small magnetic
radicals may be scavenged in the water phase (e.g., by
Cu2+ions401v407 or by Fremy's salt415)or may react to
recombination products. In the case of unsymmetrical

isotope effect at zero field, demonstrating that in HDTC
micelles the hyperfineinduced T S process is at least
of the same order of magnitude as the diffusioncon
radical pairs symmetric coupling products will be trolled intramicellar reencounter process. The magnetic
formed besides the unsymmetric ones. Thus for un isotope effect increases with the magnetic field, how
symmetric dibenzyl ketones the product distribution ever, reaching a saturation limit at about 10 mT, al
allows the fraction of cage recombination (cage effect)@l though in this field region the absolute rate constants
to be evaluated. of recombination are still strongly magnetic field de
Most of the work described by Turro with the ketones pendent. This behavior is explicable in terms of the
listed in Table 11 employed continuous photolysis relaxation mechanism as far as it is due to the stochastic
combined with chromatographic product distribution modulation of anistropic hyperfine coupling by molec
analysis. It was found that the fraction of correlated ular motion.
intramicellar recombination not only was magnetic field An interesting practical application of the micellar
dependent but also was sensitive to 13C or 'H magnetic cage effect and MFE has been reported by Turro et
isotope effects (cf. Table 11). These will be separately a1.14274149418 Emulsion polymerization of styrene and
reviewed in section 1V.H. methyl methacrylate photosensitized by dibenzyl ke
In the case of symmetrical dibenzyl ketones the tones was markedly influenced by an external magnetic
identity of cage and escape recombination product de field. Since the initial state of such polymerizations
mands different methods to assess the micellar cage starts with monomers solubilized in micelles, it is fa
effect. Useful indicators are provided, e.g., by the vorable that initiator radical pairs produced there un
quantum yield of DBK decomposition or by the effect dergo efficient escape in order to avoid fast intramicellar
of scavengers. A more direct method, however, is recombination with termination of the chain reaction.
timeresolved observation of the intramicellar radical Since the amount of escape for triplet radical pairs
kinetics by laser flash photolysis. The method has been increases in a magnetic field, higher yield and higher
applied to acleavage reactions by Hayashi and co molecular weights can be obtained under such condi
~ ~ r k eandr by~Turro ~ ~ and ~c o J w ~~ r ~ . ~~ ~ ~~ tions.
k e r~s A ~ ~~ ~ ~13C magnetic isotope effects, which have also
very detailed investigation involving several ketones of been observed can be understood by the same reason
type 34 and 36 has been reported recently by Gould et ing.
al.419 In Figure 32 is shown the MFD of the fast rate The importance of spin correlation effects for these
constant of radical decay for two of these compounds. phenomena has been demonstrated by using di
A saturation is not reached below 80 mT. B1/2values phenylazoethane (PhCH3CHN=NCHCH3Ph) as an
are approximately 10 mT, whereas the characteristic initiator of polymerization. Three modes of radical
hyperfine fields (from eq 43) are 1.5 and 3.1 mT for 34e generation have been compared, viz., thermal, direct
and 34b, respectively. photochemical, and tripletsensitized p h o t ~ c h e m i c a l . ~ ~ ~
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Voi. 89, No. 1 91
25
.K7" products are derived from radical recombination (cage
and escape) after acleavage and fast SO, elimination
;bX
zo
I5
K2:$>=
.
'
, D
vn
',Ls
'
___________9_______ ?, 
O''
e)?
'


v.c17Y.
20%
157.
(K > lo8 sl). The sulfones 38 and 39a apparently react
via their triplet state. Both direct photolysis and
tripletsensitized photolysis lead to 80% yield of cage
recombination, which is decreased by a factor of 0.5 in
,o 1 I I , , , , I I , (I , . a magnetic field of 0.3 T. With the Pnaphthylsub
stituted sulfones 39 there is 100% cage recombination
with no MFE in direct photolysis but 90% cage product
formation with a magnetic field effect of 40% in
tripletsensitized photolysis. The latter result indicates
that for 39p direct photolysis leads to singletspin
correlated radical pairs that recombine very efficiently
and, obviously, have no chance for a crossover to the
Only in the last case was a MFE observed, indicating triplet state. In contrast to the sulfones 38 and 39
that only the kinetics of initially triplet spin correlated undergoing rapid SO2elimination after acleavage, the
pairs is significantly influenced by a magnetic field. sulfone 40 investigated by Hayashi et al.398must be
A MFE on methyl methacrylate polymerization in a assumed to decompose into a radical pair (PhCOCH,'
threephase system has also been reported by Imoto and + PhSO,') where the phenylsulfonyl radical does not
Nom~to.*~ The mechanism in this case is, however, less eliminate S02,452 so that a MFE with an Scentered
obvious than in Turro's system. Other compounds radical may be studied. Using SDS micellar solution
showing a photochemical behavior similar to that de it was found398that the yield of radical escape detected
scribed in Figure 31 are the deoxybenzoins 36, the by laser flash photolysis increased by 58% in a magnetic
methyl benzyl ketones 37, and the sulfones 38 and 39. field of 1.2 T. This MFE indicates that the radical pairs
For the photodecomposition of deoxybenzoins the were formed from a triplet precursor and, what may be
MFD of micellar cage effects has been investigated in of importance for magnetic isotope separation of 33S,
some detail by Turro and Matta~.~lO In this case a that spin relaxation in Scentered radicals does not too
cleavage produces a tripletspincorrelated pair of a rapidly destroy a spin memory in the radical pair (cf.
benzoyl and a substituted benzyl radical. Cage products also section C.4 and ref 168).
are the starting materials and the disproportionation
products 58 and 59 or their respective deuteriated 3. Radical Pairs from HAtomAbstraction Reactions
h
55 56 a 56b
Ho$2
56c 56d 56e
48d 4 Be
""w 56 f 57
be shown that the quantum yield of DPBF disappear T,,S relaxation rate by magnetic perturbations due to
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 93
of the same size appears when methylviologen (MV2+ When certain dyes are adsorbed on organic crystals
(60)) is added to the system as an electron relay, al a photosensitized hole injection into the molecular
crystal may occur, causing a sensitized hole current or
sensitized delayed fluorescence. The latter process
involves electronhole recombination with formation
60 (MV2+) of triplet states, which on triplettriplet annihilation
lead to delayed fluorescence. After the primary electron
though under these conditions Hzevolution is about 40 transfer from the organic crystal to the adsorbed dye,
times more efficient. A MFE is not observed with direct
UV irradiation of the semiconductor suspension in the the charge pair originating with singlet spin correlation
absence of the sensitizer system or on the yield of M V (since S1is the photoactive excited state of the dye) may
separate, whereby the mobile species is the positive
radicals in the homogeneous Ru(bpy)2+/MV2+/EDTA
system. A reinvestigation of the homogeneous system hole, migrating by a hopping mechanism over the
in our laboratory, however, has furnished a MFE of molecules of the crystal. Since it is attracted by its
10% at 1 T on the yield of MV*+.481Recently, the image charge in the solution, the motion of the hole
remains
effect was also investigated by Ferraudi and A r g t i e l l ~ ~ ~ ~ restricted to the crystal surface for a fairly long
with high magnetic fields up to 5 T, at which the yield time.176 During this stage, there will be spin evolution
of MV" was reported to be decreased by about 27%. due to hyperfine interactions, predominantly influ
encing the fixed electron on the adsorbed dye molecule.
On reencounter of the charge pair the spins may be
2. Photoluminescence and Photoconductivity triplet aligned, suitable for recombination to produce
a triplet exciton. This situation is quite analogous to
MFEs on photocurrents in tetracene films deposited what has been described above for homogeneous solu
on anthracene crystals or silica plates were reported tions where the triplet recombination efficiency of sin
very early by Frankevich and c o  w ~ r k e r s .These
~~~ glet radical pairs can be influenced by magnetic
phenomena, which have been reviewed by Sokolik and fields.157i302
Frankevich,lZare characterized by an increase of the Merrifield and found that the de
photoconductivity in a magnetic field. The explanation layed fluorescence of anthracene, sensitized by rhoda
provided by F r a n k e ~ i c his~given
~ ~ in terms of a kind mine, xanthene, and cyanine dyes is decreased by about
of Ag mechanism operating on a loosely bound charge 50% at fields higher than 20 mT. The halffield value
pair (Wannier exciton) where singlettriplet tran'sitions of this effect was very small (12.5 mT) and was related
are assumed to be induced by different g factors of hole to the hyperfine coupling mechanism. In passing, it is
and electron. In fact, it seems to have been the first of interest to note that, historically, this MFE on de
case where the Ag mechanism was invoked. The same layed fluorescence, sensitized by hole injection, was
kind of mechanism is also thought to apply to the MFE observed prior to the corresponding case in homoge
on exciplex fluorescence observed from thin tetracene neous solutions. Also, Merrifield and coworkers, when
films on anthracene.461 The fluorescence intensity is suggesting the hyperfine mechanism for the charge
reduced by a few percent, which is the saturating MFE carrier pair in their first paper,% were not aware of the
reached at rather low fields of a few millitesla. In view obvious parallels to the radical pair mechanism that had
of the small Bl12value (1.6 mT) it appears very ques been established some years before in connection with
tionable, however, if a Ag mechanism can be a reason the CIDNP phenomenon. Actually, in this paper, they
able explanation. even argued against a possible importance of such a
Also in Frankevich's group, the rate of formation of mechanism in solutions.
photooxidation products, when t e t r a ~ e n eor~ rubr
~~ Hole injection into anthracene crystals by photoex
ene463films were illuminated in an oxygencontaining cited tetramethylrhodamine has been studied by Mi
atmosphere, has been found to be increased by a mag chelBeyerle and c o  ~ o r k e r s . ' ~They
~ demonstrated
netic field. The photooxidation rate was determined that the MFE on sensitized hole current was comple
indirectly from the intensity of a photocurrent, which mentary to that of delayed fluorescence. They also
is enhanced by the oxidation products (presumably studied magnetic isotope effects in the anthracene
aromatic endoperoxides). The MFE has been tenta crystal (H/D exchange) and in the dye (14N/15Nex
tively explained in terms of the Merrifield (TT) pair change). Only 16Nsubstitutionin the dye modified the
mechanism for the singlet channel (formation of lo2and MFE, yielding a lower Bl12value. H / D exchange in
'MO2) in the interaction of a triplet exciton with 302. anthracene was inefficient. This is explained by the fact
Since the ZFS of oxygen is rather large, a t B < 0.2 T that due to its hopping motion between anthracene
the Merrifield mechanism would predict an increase of molecules the electron hole only experiences random
the rate of singlet product formation with increasing ized hyperfine coupling, which is much less efficient
magnetic field. Geacintov and S ~ e n b e r haveg ~ ~ana
~ than a constant hyperfine coupling (cf. also section V).
lyzed the theoretical problem of MFEs on tripletaro This kind of investigation was further extended by
matic/ tripletoxygen pairs, concentrating especially on Willig and c o  ~ o r k e r swho
, ~ ~also
~ studied the depen
the energy splittings between quintet, triplet, and dence of the effects on applied voltage (cf. Figure 37).
singletpair states, which depend on the extent of The higher the electric field, the faster is the separation
chargetransfer interaction between the aromatic triplet of the hole from the electron, residing on the dye rad
and oxygen molecule. Since they failed to see a MFE ical, and the MFE on the hole current decreases.
on phosphorescence quenching of coronene, chrysene, Furthermore, using various methods of preparation of
and dibenzoanthrecene adsorbed on polystyrene fluff, the anthracene crystals, shallow traps for the injected
they concluded that the tripletsinglet splitting in such holes have been generated at the surface. These traps
encounter pairs should exceed 30 cm'. cause a characteristic change in the electric field de
96 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
0 2 c /
!
cr‘037 J
available (cf. section V).
The antiferromagnetic oxides ctCr2O3, COO, and
MnO have been investigated with respect to their
magnetocatalytic properties below and above their Neel
temperature^.^^^^^^ The catalytic activities showed
maxima at the Neel temperatures (TN),and the mag
netocatalytic effect was negative in the paramagnetic
region ( T > TN)and positive in the antiferromagnetic
region ( T < TN)(cf. Figure 38 for the behavior of a
o.+
c
\ CrZO3, which shows the most abrupt changes at the Neel
temperature).
0.4 1 I r~ Only few of the ferromagnetic solids are suitable for
1 10 102 103 to4 studies of the nondissociative p/o hydrogen conversion,
Fleld (Oe) ( l o g s c a l e ) because the dissociative route often dominates.26 For
Figure 38. Relative change of catalytic o/pH, conversion rate CrOz, EuO, and Ni nondissociative p/o hydrogen con
(Ak,) as a function of magnetic field strength for various magnetic version activity can be studied in certain temperature
materials: (a) antiferromagnetic, (f) ferromagnetic, (p) para range^.^^^^^^ It has been found that below the Curie
magnetic, and intrinsically diamagnetic substances. Reprinted temperature there is no magnetocatalytic effect,
with permission from ref 26; copyright 1985 Academic Press. whereas in the paramagnetic region these materials
show a strong, positive external MFE. Typical MFD
pendence of the MFE on the hole current.467An ap curves for the various magnetic types of the materials
propriate theoretical model has been developed ac used are shown in Figure 38. Current theories to ex
counting for the observed effects (cf. section V). plain the magnetocatalytic effects on nondissociative
p J o hydrogen conversion will be reviewed in section V.
3. Magnetocatalytic Para to Ortho Hydrogen
Conversion F. Biological Systems
Nondissociative interconversion of para and ortho 1. General Situation
hydrogen has been known for a long time to be cata
lyzed by paramagnetic collisions (e.g., with Oz,NO, and In the past many magnetobiological or magnetophy
NOz in the gas phase468and in the liquid phase with siological effects have been found and are described in
transitionmetal ions,46s473trivalent lanthanon ions,469 a number of books.58i516521The origin of most of these
and organometallic compounds47z). effects is, however, not of molecular nature or not yet
As has been shown by Wigner,82this process can be precisely known. Thus, e.g., the welldocumented
explained by the inhomogeneous magnetic field of the phenomenon of a magnetic sense of certain higher an
paramagnetic center, which exerts different influences imals, particularly of birds, still awaits conclusive
on the two proton spins of the Hzmolecule during a mechanistic explanation, though interesting hypothet
collision. So far, however, no external MFEs have been ical models have been suggested on the basis of the
reported to modify the reaction rate of this type of radical pair mechanism.514~522*523
catalytic process in homogeneous systems. On the other There are, however, specific molecular biological
hand, MFEs on the catalytic activity (magnetocatalytic systems for which MFEs have been observed in isolated,
effect)4s0have been found for several paramagnetic and welldefinedpreparations, among which photosynthetic
also some diamagnetic solids. A review of this work has reaction centers are the most prominent. The MFE
been given by Selwood,26and here we will only briefly studies of these have by now reached a high standard
consider some characteristic aspects. and will be reviewed in section 2. Other magnetic
The catalytic activity exhibited by magnetic oxides fielddependent reaction systems of biological interest
such as lanthana, lutetia, and yttria may be influenced involve cytochromecatalyzed oxidations and binding
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 97
of CO to hemoglobin. I PF 4 , PR '
Molin and c o  w ~ r k e r have
s ~ ~ ~reported that the rate 'P* I
of O2evolution in Hz02decomposition, catalyzed by the
heme enzyme catalase, is increased by about 20% in a
magnetic field of 0.8 T. Marked MFEs have been also
observed in the hydroxylation of organic substrates by
cytochrome P450, another heme enzyme. The effects
are thought to be due to the Ag mechanism increasing
intersystem crossing in intermediate Fe3+02*radical
pairs. Here &has the extremely high value of 2, which
is 1001000 times larger than in pairs of typical organic
free radicals. PI ground state
A different mechanism is responsible for the MFD
found for the rate of CO rebinding to human Phemo Figure 39. Reaction scheme of primary processes on prereduced
globin after photolysis of the adduct below 20 K. or quinonedepleted bacterial photosynthetic reaction centers.
Rather strong fields (up to 10 T) have been used to P, special pair of bacteriochlorophylls; I, "intermediate" elec
induce a weak optical linear dichroism, which is due to tronaccepting bacteriopheophytin (adapted from Werner,
Schulten, and Weller532).
anisotropically enhanced recombination of the molec
ular complex in a magnetic field.524 The MFE is due
to the fact that CO binding goes along with a highspin synthetic reaction centers. Furthermore, problems
( S = 2) to lowspin (S = 0) conversion of the complexed arising in connection with the interpretation of these
Fe" ion. The magnetic field causes changes in the ef results have instigated fundamental theoretical work
fective SOC by recoupling the quintet zerofield sub which has largely contributed to the general under
states521*526 (cf. section V.B). standing of magnetic field effects in chemical kinetics
(cf. section V).
2. Magnetic Field Effects with Photosynthetic Reaction Reviews on MFEs in photosynthetic systems have
Centers been written by Hoff37157and by Boxer et al.45 Fur
thermore, these aspects have been treated in other re
Photosynthetic primary processes occur in special views by HofP151*530531 on magnetic resonance investi
membranefixed reaction centers in the chloroplasts of gations in photosynthesis, where also a useful intro
green plants, in algae, or in several kinds of bacteria. duction to the molecular photosynthetic machinery and
Typically, the primary process is denoted as the primary processes may be found, together with a
p*1x  
2.8 ps
p*+px
5200 ps
p*+1x*
number of experimental details and references on the
preparation of suitable samples.
In this section we shall confine ourselves to tabulating
Here P denotes the chlorophyll special pair, which in the relevant experimental work (cf. Table 14) and giving
its first excited singlet states donates an electron to the a short outline of the main aspects under investigation.
"primary" acceptor X (a menaquinoneiron complex) For more details of theoretical aspects, cf. section V.
with one detectable intermediate electron acceptor I (a Most investigations in the field deal with bacterial
bacteriopheophytin in the case of bacteria) only.527 photosynthetic units, either in isolated reaction centers
Most investigations concentrate on the purple bacteria or in other preparations under reducing conditions or
Rhodopseudomonas spheroides, mainly from the car with the quinone complexes removed. MFEs were first
otenoidless R26 strain, and Rhodospirillum rubrum. detected by Blankenship et al.482and by Hoff et al.483
Recently, it has been possible to crystallize the protein on the yield of reaction center triplet. The triplet yield
complex of reaction centers of Rhodopseudomonas ui decreases in a magnetic field. The magnitude of the
ridis, a species closely related to Rhodopseudomonas effects and the halffield values are critically dependent
spheroides. It has been possible to determine the on the type of preparation of the system. Nevertheless
crystal structure and obtain detailed information on the the general results bear strong evidence that the effect
spatial configuration of the various pigments involved is due to the hyperfine coupling mechanism in the
in the primary electrontransfer ~ h a i n . In ~ native
~ ~ l ~ ~ ~radical pair. These results have prompted theoretical
photosystems electron transfer according to eq 64 is investigation^^^^^^^ studying the influence of the rate
essentially irreversible. If, however, the electron ac parameters ks and kT and the exchange interaction J
ceptor X is either reduced or removed, the primary on the MFD.
radical pair P ' T may undergo electron backtransfer In order to understand the relatively large Bl12value
in various ways represented in Figure 39. Whereas the in some preparations, which considerably exceeds the
singlet ground state P can be regenerated directly, a value of the typical hyperfine coupling strength in the
multiplicity change in the radical pair PF is necessary radical pair PF,Werner et al.532included the effect of
to allow for (reversible) formation of the triplet state the electron backtransfer (rate constant k h) leading
PRof the special pair, which is energetically somewhat to repopulation of the excited singlet state. In fact, such
below the radical pair state. From the singlet pair, a reaction should give rise to a MFE on the delayed
electron backtransfer to regenerate the excited singlet fluorescence, which actually has been ob
state has to be considered, too. ~ e r ~ e d . ~ The ~ ~ effects
 ~ ~on~the* total
~ ~fluores
~ s ~ ~ ~ * ~
In view of the general interest in the molecular cence yield are rather small since most of the fluores
mechanism of photosynthesis, great effort has been cence is prompt fluorescence from antenna bacterio
applied to utilize MFEs on triplet formation, ground chlorophylls. The effects on the delayed componentm
state repopulation, and delayed fluorescence in photo are, however, of the same magnitude as on the yield of
98 Chemical Reviews, 1989, Vol. 89, No. 1 Steinsr and Ulrich
TABLE 14. Magnetic Field Effect with Photosynthetic Reaction Centers ~ ~~~
Photosynthetic bacteria: Rps. sph., Rhodopseudomonas spheroides; R26, carotinoid less mutant of Rps. sph.; Rsp. r., Rhodospirillum
rubrum; RC, isolated reaction center protein complex; Q , quinone constituent of RC. A, absorption spectroscopy under steadystate illu
mination; Bo", modulation of Bo field; F, stationary fluorescence; trF, timeresolved fluorescence; LFP, laser flash photolysis; TPLFP,
twopulse laser flash photolysis. IF,IDF, intensity of fluorescence, delayed fluorescence; MFD, magnetic field dependence, unless otherwise
stated of case 1 type (specified by Rs, Bs, Bllz;cf. Figure 6); MODS, magnetooptical difference spectroscopy; PR,special pair triplet; PF,
radical pair P'+I'; AR change of R due to resonant microwave (MW) irradiation; R( ) relative change of specified quantity; 7 , delay time of
probing pulse; T ~ T,( X ) time constant of process X, or lifetime of species X.
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 99
PR,i.e., up to several 10%. Rademaker and Hoff5= have Boxer and c o  w o r k e r have
~ ~ ~also ~ ~ ~ a signif
~ ~ found
set up a general kinetic scheme relating the results of icant magnetic anisotropy of the effect when using
theoretical model calculations to the quantities actually bacterial reaction centers suspended in highly viscous
observed under experimental conditions. This work media. The magnetic anisotropy is borne out in the
demonstrates that, in principle, the hyperfine coupling comparison of measurements with the magnetic field
mechanism can account for the effects observed. axes parallel or perpendicular to the electric field vector
Under conditions of continuous illumination a certain of the exciting light. The anisotropy of electron spin
fraction of reaction centers will be in the PRstate with spin interaction in the radical pair or a Ag anisotropy
a concomitant depletion of the ground state P. The was considered as a possible reason for this effect.
magneticfielddependent rate of PRpopulation will be Recent theoretical results obtained by Ogrodnik et
reflected in a corresponding MFD of the PRsteadystate for the spindipolar interaction between the various
concentration. Such effects have been utilized by radical species based on the crystal structure data of
Chidsey et al.488and by Norris et a1.495to investigate Deisenhofer et al.528indicated that this type of inter
the MFD of PRformation yield. Furthermore, the MFE action is probably too weak to be extracted from mag
on steadystate concentrations of PRand P can be ex neticfielddependent reaction fields (MARY) or
ploited for sensitive monitoring of the AOD spectrum RYDMR experiments.
of these species. The method has been systematically Recombinations to the ground state P (rate constant
developed as a novel spectroscopic technique (MODS k s ) and to the triplet state PR (rate constant 121.) rep
(magnetooptical difference spectroscopy)) by Hoff and resent the main decay channels of the radical pair PF.
co~ o r k e r ~ . ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ From the sign of the MFE on the triplet yield it follows
MichelBeyerle et al.15s@1have investigated the MFE consistently that kT must be larger than ks. This re
on the yield of PRdetected at variable delay time after lation is also borne out in the results of PFlifetime
the photolyzing laser pulse. Their results exhibit a measurement^.^^^^^^^ Chidsey et al.511found that the
lifetimebroadening effect whereby the BlI2values in lifetime of PFincreases at low magnetic fields, reaching
crease as the delay time is decreased in the nanosecond a maximum at about 0.1 T, and decreasing again to a
region. The observed MFD of PRyield has been re value that at B = 5 T is even smaller than for zero field.
produced by a theoretical model employing two sites Since, according to the radical pair mechanism, the
of the intermediate acceptor radical I*. This model had singlettriplet conversion rate is slowed down at low
been suggested by Haberkorn et a1.534in order to ex fields (hyperfine mechanism) and increased in high
plain an obvious discrepancy between the electronic fields (Ag mechanism), it follows from the MFD of the
matrix element of the forward electron transfer PFlifetime that the triplet radical pair decay to PRmust
(whereby PF is formed) and the upper limit of a few be faster than the singlet radical pair decay to P. A
gauss for the exchange interaction in PFderived from MFE that parallels the effect on the yield of PR has
the MFEs. It was suggested that the radical electron been also found on the lifetime of PR.510v511 The MFE
on 1' is exchanged between two sites with different on PRlifetime disappears a t low temperature. These
separation from the special pair radical Po+.This view results indicate that at room temperature PRdecays to
has been supported by recent Xray diffraction results, a considerable amount through thermally activated
showing a bacteriochlorophyll between the special pair formation of PF. From the temperature dependence of
and the bacteriopheophytin molecule which is adjacent the effect a reaction energy of 0.12 eV has been ob
to the menaquinoneFe complex. However, recent tained.
timeresolved experiments with an 80fs time resolu There have been attempts to observe H/D magnetic
tion527afforded no evidence of the involvement of the isotope effects on the yield of triplets from charge re
accessory bacteriochlorophyll as a transient electron combination in reaction center triplet^.^^^,^^ Surpris
acceptor. Furthermore, in a recent paper by Ogrodnik ingly, no deuterium effect on the yield of PRoccurred.
et al.515it was derived from the weak temperature de In comparison with bacterial photosynthetic reaction
pendence of k T that the electronic matrix element re centers there are rather few investigations available
sponsible for forward electron transfer is about 25 times dealing with MFE studies in photosystems of plants.
larger than for backtransfer (whereby PRis formed). Fluorescence investigations of preparations showing
Since Haberkorn et al.,5%when suggesting their twosite preferential delayed fluorescence of either photosystem
radical pair model, had started out from the assumption 1494p499 or photosystem I1491y492
have revealed, however,
of equal matrix elements for electron transfer in both that similar MFEs as observed in bacterial reaction
directions, their interpretation is inconsistent with the centers occur in photosystems of plants, too.
recent findings. The asymmetry of the coupling ele In the reaction sequences of Figure 39 or eq 64 the
ments of forward and backward electron transfer is radical pair state PF is normally too shortlived to be
attributed to a socalled superexchange mechanism, directly detectable by ESR spectroscopy. However, in
where the accessory bacteriochlorophyll functions as a the case of prereduced primary acceptor X spin po
virtual electron relay. larization developing during the lifetime of PF may be
Since Ag in PF is of the order of 0.001,488the MFE transferred to the paramagnetic species 2x*or 3P (=PR)
is of case 1 type up to fields of 0.1 T. A dominating and may be used to derive information on magnetic
contribution of the Ag mechanism was, however, es interactions during the lifetime of PF. Furthermore, in
tablished by Boxer et a1.,4881503 who applied magnetic the case of nonprereduced X, the secondary pair Po+
fields up to 5 T. Thus, whereas the triplet yield is IX* may be conveniently studied by ESR since its
significantly decreased in low fields, in the highfield lifetime is of the order of millisecond^.^^' For a survey
region the yield of PRmay be even increased above the of the literature on electron spin polarization cf. the
zerofield value. Although the radical pair
reviews by Hoff.34~44~51*57*530~531
~
100 Chemical Reviews, 1989, Vol. 89,No. 1 Seiner and Ulrich
anthraceneTCNB EDA PC D+D AR(ipc) < 0, single line, AB = 1.7 mT Frankevich et al."'
complex, polycryst
sgl cryst DF T+T AR(ZDF) > 0, two lines, level crossing on rotation Lesin et al."2
about c axis (LBO)
AR(ZDF) sign change on rot about b axis ( L B O )line
, Frankevich et al.MgM6
inversion at high MW power: double transitions
P, DF T+T at 1.2 K: AR,line doublet, inversion at high MW Steudle and v. SchutzM
power
AR(ZDF), dep on delay between excitation/RF v. Schultz et aLBO
pulse/detection
anthraceneDMPI EDA DF T + T, AR(ZDF) > 0, broad triplet (ZFS), reson with Frankevich et al.M69"7
complex, preexposed to T+D narrow doublet reson (AR(ZDF) < 0)
yirradiation superimposed
Radioluminescence
naphthalene in squalane trRL, 22Nap+ D + D AR(ZRL) < 0, unresolved line, intensity depends on Anisimov et al.:1,548
MW power Molin et a1.'%
biphenyl in squalane trRL, %r ,T D+D AR(Z,) < 0, HF structure resolved Molin et al.125~Mg
pyrene or biphenyl in decalin trF, PR D+D AR(ZF) < 0, FDMR rise time 50100 ns Trifunac and Smiths2
PPO or biphenyl in AR(Z,) < 0, trFDMR, biphenyl: HF resolution Smith and Trifunacm
cyclohexane at low MW powers
anthracene or biphenyl in AR(ZF) < 0, H/D isotope effect on FDMR rise time Smith and T r i f u n a P
cyclohexane
C6F6in squalane trRL, gOSr i3 D+D AR(ZRT.) < 0, secondorder resolved HF structure of Anisimov et alFS2
c6Fi radical
fluoro aromatics, TEA + RL D+D AR(ZRL) < 0, HFresolved spectra Molin and Anisimoe3
durene or anthracene dlo
in squalane
pterphenyl, PPO, F, Xray D+D AR(ZF! < 0, HFresolved spectra of secondary Melekhov et al.6M
naphthalene#* in decalin, radical cations
cyclohexane, isooctane
C6F6,biphenyl, naphthalene RL D+D AR(Z,) < 0, determination of iontomolecule E T Saik et alam
in squalane rate const from HF line width
durene in squalane RL, Xray D+D AR(ZRL) < 0, e and durene+ RYDMR detectable Molin et al.m
on addtn of traces of water
pterphenyl in benzene AR(ZRL) < 0, RYDMR spectra of benzene+ radical
ion at low pterphenyl concn
alkylamines with PPO or F, PR D+D AR(ZF) < 0, 'H and "N HFresolved RYDMR Leflcowitz and
anthracene in nhexane, spectra of aminium radicals Trifunacm
cyclohexane
triethylamine in F Xray D+D (7' = 119 and 150 K): AR(ZF) < 0, RYDMR int Smirnov et a1.%'
3methylpentane dep on e + TEA+ recombination time
Laser Flash Photolysis
anthracene + DEA in ACN LFP D+D AR(3Ac rise time) < 0 with B1 = 11.6 mT, AR > 0 Wasielewski et al.lZ3
with B1 = 32.6 mT
pyrene + DMA in SDS LFP D+D MW depdt transient absorptn signals from 3Py Grant et al.12'
micelles and Py'
Rps. sph. R26, quinone LFP D+D AR([PR])> 0 (low MW power), < 0 (high MW Bowman et a1.,lZ2
depl RCs power), narrow line on broad background Norris et aleWB
TS background attributed to triplet ODMR (at room Norris et aL512
temp)
D+D AR([PF],5 ns) < 0, AR([PF],200 ns) > o Wasielewski et
Rps. sph. R26, quinone LFP D+D AR(PF lifetime) < 0 (low MW power), AR > 0 Wasielewski et aL508
depl RCs (high MW power)
Rps. sph. R26, quinone LFP D+D lowpower, lowfield RYDMR: AR([PR]),temp dep Moehl et al.'07
reduced or depleted RCs of spectra (cf. Figure 41)
(IDEA, Nfldiethylaniline; DMA, N,Ndimethylaniline; DMPI, pyromellitic N,"dimethyldiimide; EDA, electron donoracceptor; PPO,
2,5diphenyloxazole;Rps. sph. R26 RC, Rhodopseudomonas spheroides R26 strain reaction centers; SDS, sodium dodecyl sulfate; TCNB,
1,2,4,5tetracyanobenzene; TEA, triethylamine. DF, delayed fluorescence;F, fluorescence;LFP, laser flash photolysis; P, phosphorescence;
PC, photoconductivity; PR, pulse radiolysis; RL, radioluminescence; tr, timeresolved. AC, anthracene; CT, charge transfer; AR(X), in
tensity of RYDMR line, monitored through quantity X FDMR, fluorescencedetected magnetic resonance; HF, hyperfine; Z, luminescence
intensity; ipc, photocurrent; MW, microwave; PF, primary radical pair in photosynthetic reaction center; PR, triplet of photosynthetic re
action center; ZFS, zerofield splitting.
RYDMR effect ensues that is opposite to the static of the radicals the static magnetic field couples S and
MFE (MARY effect). Toradical pair states, resonant microwave transitions
On the other hand, if by virtue of a gfactor difference to or from Towill support the kinetic flow from S to the
102 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
an external magnetic field, encounters of charge carriers reported are based on the radical pair mechanism.
with parallel spins, which cannot recombine, will be a There are two principal cases in which MIEs can be
little more probable than encounters with antiparallel observed:
spins, which can lead to recombination. Resonant (a) When magnetic (nonmagnetic) nuclei are substi
microwave absorption will decrease the bulk spin po tuted by nonmagnetic (magnetic) isotopes, changes in
larization and hence increase the recombination prob the behavior of chemical compounds may be found
ability. This model, however, underestimated the ob which are shown in different zerofield reaction yields
served effects by 12 orders of m a g n i t ~ d e . ’ ~ ~ and kinetics, as well as in the MFD of these quantities.
That the situation in spindependent charge recom Such comparative studies have been performed with
bination is completely analogous to the radical pair H/D substitutions in a number of cases (cf. Table 16)
mechanism with recombining F pairs in chemical ki but also with some 12C13C substitutions.146@5~4M~424~42
netics was not recognized a t first, and the motion of (b) If compounds containing isotopic mixtures, e.g.,
correlated spin pairs and the idea that an excess of of natural abundance (cf. Table 16), are subjected to
tripletspin correlated pairs is produced as a conse reactions involving radical pair intermediates, the dif
quence of spindependent recombination was intro ference in hyperfine coupling of the corresponding
duced as a mechanism of its own by Kaplan et a1.,573 isotopes will cause a different distribution of isotopes
who treated this situation within a semiclassical model. between cage and escape product channels, so that
The connection with current theories of RYDMR in chemical isotope separation takes place, leading to
radical pairs was established later by Haberkorn and magnetic isotope enrichment in either cage or escape
diet^^^^ (cf. section V). product, whichever requires a radical pair multiplicity
In concluding this section we wish to note that not change in order to become more favorable.
only resonant microwave but also radiofrequency The characteristics of MIEs have been explicated in
transitions may be used to modify the reactivity of some detail by B u c h a c h e n k ~ It. ~must
~ ~ ~be~ empha
~
radical pairs. Such effects are detectable by a change sized that MIEs can be much larger than mass isotope
of CIDNP intensities in the products formed from the effects. L a ~ l e rhas
~ ~formulated
l three criteria to dis
radical pairs wherein the nuclear transitions occur. The tinguish between mas and magnetic isotope effects:
method was first applied by Sagdeev et a1.’l0 to pho (i) Whereas mass isotope effects depend monotoni
tochemical reactions carried out directly in the probe cally on the mass of the isotopes to be compared, such
of an NMR spectrometer. Analogous experiments with a relation does not exist for the MIE. A particular case
radical pairs from pulse radiolysis were performed by where this has been put to test by Turro et al.148,460 is
Trifunac and E v a n o c h k ~ . ~These
~ workers used a the 0 isotopes l60, 170,and l80, where only the middle
further developed technique employing a flow system one is magnetic.
that allowed them to perform radical pair NMR in a (ii) MIEs are highest in zero magnetic field or at low
separate magnetic field before the sample was trans field strength comparable to the hyperfine coupling
ferred to the NMR magnet wherein the CIDNP signal constant of the isotopic atom under consideration (for
was detected. CIDNPdetected magnetic resonance of experimental examples, cf. Turro et a1.407,408).
radical pairs is a kind of ENDOR spectroscopy. Hy (iii) MIEs change sign if the multiplicity of the radical
perfine coupling constants and kinetic parameters of pair precursor is changed between singlet and triplet.
radical pairs can be obtained from it. These criteria follow from the radical pair mechanism
Another most remarkable example of NMRinduced in a straightforward manner.
rate enhancement of radical reactions has been reported As was noted by Buchachenko,50one should be aware
by Yurke et for the reaction of electronspinpo that MIEs could be well responsible for unusual isotopic
larized hydrogen ( H i ) at low temperature. In a mag distributions in geochemical and cosmic material, and
netic field the lowest two hyperfine levels “a” and “b” the hypothesis of chemical fractionation should not be
correspond to a pure triplet alignment of electron spin discarded on the basis of considering mass isotopic
and nuclear spin (b) or an approximate 50/50 S/T effects only.592 In fact, Haberkorn et al.582have dis
mixture (a). On the other hand, the electronicnuclear cussed the possibility that the radical pair mechanism
spin wave function of groundstate molecular ortho/ might account for an unusual 13C isotope enrichment
para hydrogen does not contain contributions of atomic in the Hadjacent carbon position of cyanoacetylene
b X b products. Therefore only the collisions Hl(a) detected by microwave spectroscopy in interstellar
Hl(a) or Hl(a)Hl(b) can lead to recombination, which molecular
means that Hl(a) is preferentially depleted and a nu Magnetic isotope separation or enrichment is of ob
clear spin polarization (surplus of Hl(b)) ensues, to vious interest in itself, but also as a mechanistic tool
gether with a slowing down of the recombination rate for probing the kinetics of radical pair

as the fraction of Hl(b) grows. NMR transitions HJ.(b)
Hl(a) will then increase the recombination rate
again. This effect has been observed at 0.23 K in a
As such, magnetic isotope enrichments have an advan
tage over MFE investigations in that they do not re
quire comparison of experiments with zerofield refer
magnetic field of 8.3 T. ence experiments carried out under otherwise exactly
identical conditions. Only the isotope distribution of
H. Magnetic Isotope Effects some product (or the educt after stopping the reaction)
has to be compared with that of the educt (before the
Whenever multiplicity changes due to hyperfine reaction). According to B u c h a ~ h e n k o ,two~ ~ basic
coupling receive kinetic relevance in a step of a reaction schemes ((65) and (66)) for magnetic isotope separation
mechanism, magnetic isotope effects on overall reaction may be distinguished.
rates, quantum yields, or chemical yields are to be ex In case of scheme 65 escape product (EP) and cage
pected. So far all effects of this kind that have been product (CP) formation are irreversible, and hence the
104 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
relative isotope enrichment of CP and EP is inde In case of scheme 66 radical pair formation from a
pendent of the degree of conversion of A. starting material A is partially reversible (cage recom
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 105
this case. An appreciable natural abundance of 13C triplet pairs, and hyperfine coupling of terminal 170
allows the use of natural material and easy detection atoms will favor tripletsinglet transitions in these pairs
of enrichment by NMR spectroscopy. The preferred so that tetraoxide formation takes place more effi
model compound to study the 13Cmagnetic isotope has ciently. Consequently, molecular oxygen evolving from
been dibenzyl ketone (33), the reaction pathways for subsequent tetraoxide decomposition will be enriched
photolysis of which have been given above (cf. Figure in 170.
31). Remarkable progress in this field was made by the Magnetic isotope effects of heavier elements would
discovery of the micellar supercage effect,402whereby be certainly of great practical interest. Since effects of
enormous enhancements of the singlestage enrichment nuclear magnetic moments on radical pair kinetics re
factor could be achieved, amounting up to a = 1.47.402*405 quire the absence of spin relaxation processes, which
In principle, efficient magnetic isotope enrichments are due to other interactions involving, e.g., spinorbit
should be also expected for reactions involving long coupling, which increases strongly with nuclear charge,
chain biradical intermediates. With this intention this seems to restrict the range of applicability of the
Klimenko et al.580investigated the 13C enrichment in MIE to lighter elements. So far, there seems to be no
cyclododecanones upon reversible photolysis. The en definite report on MIEs with elements heavier than
richment factors were, however, not extraordinarily oxygen, although there are indications that germani
high, which was attributed to a low reversibility of bi um29192927426
and s u l f ~ r  c e n t e r e radicals
d ~ ~ ~ are capable
radical formation in these systems. of preserving spin memory sufficiently long that hy
The micellar supercage effect and its sensitivity to perfine coupling effects may develop. A magnetic iso
magnetic isotope effects have also been exploited for tope effect reported by Molin and c o  w o r k e r ~for ~~~
emulsion photopolymerization, where a significant '17Sn and l19Sn was disproved by them later.596
isotope effect on molecular weight distribution has been
found by Turro et aL414Furthermore, enhancement of V. Theoretical Studies
cage effects due to restricted diffusion on surfaces has
also been demonstrated to be favorable for 13Cenrich A. Mechanisms in the Gas Phase
men t.460
Apart from acleavage reactions of ketones, 13C Cage effects in the gas phase are generally negligible.
magnetic isotope effects have also been shown to occur Therefore, except for the case of biradicals (cf. section
in the photoreduction of benzophenone in micellar so IV.A), mechanisms of the paramagneticpair type can
l u t i o n ~ Tripletsensitized
. ~ ~ ~ ~ ~ ~ decomposition
~ ~ ~ ~ ~ of not operate under gasphase conditions. Magnetic fields
dibenzoyl peroxide was one of the first examples of 13C may influence intramolecular radiationless transitions
e n r i ~ h m e n t . Thermal
~~ decomposition of this com only, either in isolated molecules or in collisioninduced
pound leads to singlet pairs, which may recombine in processes, where intramolecular couplings provide for
a spinallowed process to yield only minor 13Cenrich the mixing of different electronic manifolds and colli
ment.50 sions provide the energy to compensate for rovibronic
Another series of examples of magnetic isotope en energy mismatch between different electronic states in
richments of a fairly light element have been reported small and intermediatesize molecules.597599Theory
for 1 7 0 . One type of reaction is thermolytic decompo of MFEs on excitedstate decay of molecules in the gas
sition of endoperoxides, which has been investigated by phase is intimately related to the theory of radiationless
Turro and c o  ~ o r k e r s . Thermolysis
~ ~ ~ , ~ ~ ~ of compound processes. It will generally require a detailed consid
3 yields lo2and 302.As to be expected, the magnetic eration of molecular electronicrovibronic states and
isotope I7O is enriched in 302, whereas the nonmagnetic level schemes.
isotopes l60and l80have a slight preponderance to be Whereas in the pair mechanisms and the triplet
found in the singletoxygen trapping product. These mechanism when applied to condensed phases only spin
experiments represent an example of a magnetic isotope motion is treated fully quantum mechanically, in which
effect with a trio of isotopes where the middle isotope an effective spin Hamiltonian is used and the electronic
is selectively enriched due to its magnetic properties, orbital dynamic variables are treated in a phenomeno
as anticipated by Lawler's first criterion (vide supra). logical manner, the explicit Zeeman Hamiltonian is
The radical pair intermediate in the thermolysis of generally applied in the treatment of gasphase MFEs.
endoperoxides must be a diradical species, and it is
remarkable that hyperfine coupling effects can establish H,(L,S) = peBo(L + 2 5 ) (76)
themselves against the strong exchange interaction to
be expected in these systems. Lin and FujimuraZ9have considered an extended form
Enrichment of 170has been studied by Buchachenko including also diamagnetic interaction:
and c o  w o r k e r ~ in~ ~some
 ~ ~oxidation reactions with
molecular oxygen. The substrates used were hydro HZ= Hz(L,S) + eo2/&" x Bo2C(xL2
+ yL2) (77)
1
carbon polymers and ethylbenzene. Enrichment of 170
is detected in the recovered oxygen in the gas phase. The index i runs over all electrons of the molecule.
Magnetic isotope selection in these systems is believed For states characterized by the quantum numbers
to occur during encounters of free peroxy radicals (cf. lJKMSZrel),where J is the total angular momentum,
scheme 75). F pairs are known to behave similarly to M its projection onto the laboratoryfixed z axis (par
allel to Bo),K its projection onto the molecular axis, S
ROOOOR  02 + products the electronic spin, Z its projection onto the molecular
2R02'  1*3mOi*02R)
E
Xi
RO2' 
R' H
ROOH
(75) axis, and relthe irreducible representation of the
electronic orbital wave function, the following selection
rules for magnetic coupling ( \kilHZl\kf)are valid:223,600
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, NO. 1 107
11) if) 11) (11 (f) II> 111(11 (f) +
element (uo u B ) ~ will
, depend on the sum of a linear
and a quadratic term in the magnetic field Bo. Orien
tational averaging, however, cancels the linear term.
Thus, the square dependence of the magnetic field is
looked upon as the characteristics of the direct mech
anism, which, according to Lin and F u j i m ~ r acorre
,~~
sponds to the purely intramolecular mechanism.
a) b.cl dl
In case b, the socalled indirect mechanism of Atkins
and Stannard,G1the magnetic field perturbation couples
Figure 42. Scheme of coupling cases serving as a basis for ex the initial state to a sparse manifold of intermediate
plaining magneticfielddependent decay of excited states in the states that undergo final irreversible decay by colli
gas phase; cf. text. sioninduced quenching. Here the magneticfieldde
pendent increase of the coupling leads to an increasing
AS = 0 (784 contamination of the initial states with one or a few
intermediate states, an effect that saturates at high field
when the coupling strength exceeds the energy sepa
ration between initial and coupling intermediate states.
Here, too, the magnetic field dependence starts with a
B2 behavior but soon reaches a saturation limit. It must
be emphasized that, although collisions are necessary
to render the process irreverisble, the mechanism of the
MFE is essentially an intramolecular one.
rel,i= rel,fif A 2 # 0 (780 Mechanism c, explained in the same level scheme as
mechanism b, is based on a magnetic shift of initial or
These rules correspond to those given by de KronigGol intermediate states; i.e., the Zeeman interaction is di
for spinrotational coupling except for the extension of agonal in the li) and/or (1) basis. In such a case the
the A J = 0 selection rule to A J = 0, fl, indicating that energy separation between coupling levels is variable
molecular angular momentum does pot have to be with the magnetic field and typical resonance phenom
conserved in an external magnetic field. ena should occur. This type of mechanism has been
As an important consequence of the selection rule termed the “energy mechanism”.600
(78a) it should be noted that a magnetic field cannot Finally, type d is also a subcase of the indirect
directly mix states of different multiplicity ( A S = 0). mechanisms. It comprises a requantization of the
Nonvanishing singlettriplet mixing matrix elements sparse manifold (1) to (19, e.g., a change of quantization
due to Zeeman interaction may be, however, invoked of the electron spin from the molecular coordinate
in higher order perturbation theory. Thus MinaevGo2 system to the laboratoryfixed system, a phenomenon
advocates efficient ~ I I I I * / ~ ~ coupling
II* via secondor similar to the PaschenBack effect in atomic spec
der combined spinorbit/magnetic (15)coupling through troscopy. This mechanism, too, is characterized by a
the intermediacy of a mr* state. saturating MFD, which makes it possible to draw con
Radiationless processes require that the discrete in clusions about the strength of the spin coupling to the
itial states are directly or indirectly coupled to a qua molecular frame. As will be seen from the discussion
sicontinuum. There are various types of coupling below, explaining the MFD of the decay rate of li) by
schemes that may serve to classify the mechanism of this mechanism is by no means an obvious matter.
a MFE, although one should keep in mind that this In what follows, we shall briefly survey the applica
mechanistic classification may be somewhat arbitrary tions of these theoretical models to the experimental
since it depends on the choice of the quantum me examples of MFEs in the gas phase outlined in section
chanical basis set. 1V.A. For previous reviews on the field, cf. the articles
Figure 42 gives a schematic illustration of the various by Kuttner et al.24and by Lin and F u j i m ~ r a . ~ ~
coupling schemes considered. li) denotes the initial The bestinvestigated case of the direct mechanism
discrete state, ( f l the final quasicontinuum, and ( I ) or (case a) is the magnetic predissociation of iodine. The
(19 sparse manifolds of intermediate states. uo denotes first thorough theoretical treatment of this problem was
a coupling element independent of magnetic fields given by van V l e ~ kwho , ~ ~showed
~ that the emitting
whereas uB is a coupling element proportional to the B3110+,state is magnetically coupled to the dissociative
strength of the magnetic field, uc denotes an effective ’&,,state. The coupling is actually due to the different
average coupling element between intermediate states gyromagnetic ratios of orbital and spin angular mo
and final quasicontinuum (including also the effect of mentum and bears some analogy to the Ag mixing of
collisions), and EB is a Zeeman energy shift. The types To and S in radical pairs. Using the golden rule ex
of mechanism presented in Figure 42 summarize the pression for the rate constant of predissociation and
rather similar models independently suggested by At applying orientational averaging, the following ex
kins and Stannard,6lPm Matsuzaki and Nagakura,m and pression was derived, valid for highly excited rotational
Lin and F ~ j i m u r a . ~ ~ levels:
Mechanism a entails a direct coupling between the
initial state li) and the manifold (A whereby the mag
netic field may couple li) and Lfl only if they are of the (79)
same multiplicity, as follows from selection rule (78a).
The rate of decay of ti), which, according to the golden There was not enough spectroscopic information
rule, is proportional to the square of the coupling matrix available at that time to estimate the FranckCondon
108 Chemical Reviews, 1989, Vol. 89, No. 1 Seiner and Ulrich
B. The Triplet Mechanism where the ca,i are the elements of the transformation
matrix relating the (xyz)to the (ucl) basis. One should
A general kinetic framework for theoretical treat note that the transition from eq 89 to eq 91 does not
ments of the triplet mechanism is provided in Figure simply correspond to a change of the basis, but, in ad
44.160 The choice of the triplet substates T,, T,, and dition, to a neglect of the offdiagonal density matrix
T,, used to describe the dynamical situation, is not elements after the basis transformation. Actually, this
unique and is suggested by the way one prefers to vis point is essential in order that spin polarization can
ualize the process in a semiclassical picture. Of course, result when, in a final step, the density matrix is pro
the underlying physics must be independent of the basis jected onto the (+&) basis, appropriate to describe the
set chosen. In general, T,, T,, and T, are not identical spin state after dissociation of the triplet into a radical
with the actual eigenfunctions of the spin Hamiltonian pair. Projecting, instead, in a nontruncated way directly
H in an arbitrary external magnetic field, but rather from the selectively populated ( x y z ) basis of the triplet
with the eigenstates of some limitingcase spin Ham onto the (+&) basis of the radical pair would produce
iltonian Ho (e.g., zero field (HD) or high field (Hz). no spin polarization. Schematically the spin polariza
Then, there will be coherent transitions among the tion mechanism may be expressed by the following
triplet substates due to their coupling by (HHo),which shorthand notation:
is indicated by the “resonance” arrows in the scheme
of Figure 44. Furthermore, due to a stochastic modu
lation of H , especially by the tumbling motion of the
truncation truncation
molecule, there will be incoherent transitions among the
substates, represented by wavy arrows and theoretically (92)
dealt with by a superoperator R acting on the triplet It has been pointed out by ElSayed and Leyerlem that,
spin density matrix p. Sublevelselective population is if singlettriplet intersystem crossing populates T,in
represented by the operator WT, and chemical decay directly via T2,the polarization could be different from
and ISC to the singlet ground state are represented by the case where Tl is populated directly, because the ZFS
the operators Kp and Ks, respectively. A general parameters may be different in the two electronic states.
110 Chemical Reviews, 1989, Vol. 89, No. 1 Seiner and Ulrich
The central part of scheme 92 would then have to be stant k, characterizes the nonsublevelselective decay
replaced by of the triplet to radicals, wherein the spin polarization
 p(diag),fc,l,

u'c'l' ucl
p(diag),,l (93)
is to be probed. In eq 95 only sublevelselectivetriplet
population is considered. The source term is propor
diagonal
truncation tional to the concentration of decaying excited singlets
(exp(k ' t ) )and its sublevel selectivity is described by
In the more advanced theories of the triplet mechanism a rate constant operator KT(Q),which is assumed to be
as applied to CIDEP604611or to MFEs on product diagonal in the same moleculefixed basis as HD(Q).
yields80J60~335~612 the spinsublevelselective population The ZFS Hamiltonian HD(Q) has been represented by
or depopulation term is assumed to be diagonal in the
( x y z ) basis independent of the strength of the external HD(0) = sD(n)s (96)
magnetic field. Then it may be shown, as has been where D(Q>is a traceless tensor that may be charac
nicely illustrated with a vector model by H ~ r e ,that ~l~ terized by constants D and E related to the diagonal
spin polarization is not produced instantaneously, but elements in the main axis system by
requires a time span in the order of one Larmor pre
cession period before the nondiagonal elements in the D = '/zZ(Dxx+ Dyy) D,, (974
(ucl) basis have decayed by phase randomization.
Felix and Weissman614raised the question of a pos E = yz(Dxx  Dyy) (97b)
sible interference of { SIIHs,ITlxb,))coupling elements
in a magnetic field when the ( x y z ) substates are re It has been convenient to introduce irreducible tensor
coupled to (ucl) states. Applying the golden rule ex notation (for details of this formalism, cf. the books by
pression, one would relate the zerofield rates wTi (i = Fano and Racah,620Edmonds,6'l and Rose622)whereby
x , z ) to the fielddependent rates wTrr ( a = ucl) by an eq 96 adopts the following form:
expression of the type 2
HD (Q) = (1)QDQ(2)(
Q) Sg(2) (98)
WTa = Ic,,i12wT,t + ~ ~ , , ~ ~ * , J ( W T , C W T J )(94)
~'~ Q=2
1=r,y,z C#J
The components of the secondrank tensor operator S2)
The analysis of triplet population and depopulation are defined by eq 99. (Note that there are some mis
kinetics measured by Felix and Weissman did not prints in ref 609.)
support the necessity to take interference terms, cor
responding to the second sum in eq 94, into account. sow= (3/2)1/2(S,2 @/3) (994
As with the radical pair mechanism, theories of triplet
mechanism type CIDEP and MFEs on product yields
are closely related. Whereas, however, CIDEP effects
may arise from both spinsublevelselective popula s*z (2) = 1/zss, (99c)
tion15i79and/or d e p o p ~ l a t i o n " ~of, ~a ~reactive
~ triplet
state, MFEs on product yields will ensue only in the The coefficients DQ(''(Q)are given by
case of spinselective d e p o p u l a t i ~ n .The ~ ~ ~kinetic
~~~ + E(Dfb(Q)+ D!\!Q(Q))
DJ2'(Q) = (2/3)1/2DD62b(Q)
treatment of the triplet mechanism under conditions
of isolated triplet sublevels (i.e., negligible spinlattice (100)
relaxation) at low temperatures is straightforward and The angular dependence is expressed through the ele
has been applied in several cases to experiments probing ments of the Wigner rotational matrices D$)Q(Q)(cf. ref
the triplet lifetime.228,280~484~618,619Astonishingly, except 620622).
for some qualitative speculations published in 1972 by The spinselective kinetic operator KT(0) is expressed
Gupta and H a m m ~ n d ~ ~on~ a@possible * participation in a form isomorphic with eq 98, but including an ad
of this type of mechanism in tripletsensitized cistrans ditional isotropic contribution:
isomerizations of olefins, the principles of the triplet
mechanism were not applied before 198080p335 to explain
MFEs on product yields in liquid solutions, several
years after profound theories of triplet mechanism type where kT is given by
CIDEP had already been developed.
The first dynamical treatment of the triplet mecha hT = 1/3(kTx + hTy + kTz) (102)
nism as applied to CIDEP in liquid solution was worked
out by Atkins and E v a n ~ . " ~Their , ~ ~ ~treatment was The function KQ(2)(Q)
is of the form of eq 100 but with
based on the following stochastic Liouville equation: D and E replaced by Dk and Ek, given by
p = HZ + H~(fi),p]..  kpp + KT(Q)exp(k't) (95) Dk = '/Z(kTx + kTy)  kTz (103a)
The triplet spin density matrix p is represented in a
laboratoryfixed system of reference and therefore the
ZFS operator HD is a function of the molecular orien In order to obtain an approximate analytical solution
tation, represented by the set of Eulerian angles Q ( t ) , for the ensembleaveraged timeintegrated density
which undergo stochastic changes due to the rotational matrix, eq 95 was transformed to the rotating frame and
diffusion of the molecule. Since spin relaxation is converted into an integrodifferential equation by formal
mainly due to this stochastic process, an explicit ex integration and resubstitution of the result into the
pression separately accounting for spin relaxation does differential equation. Ensemble averaging was per
not appear at this stage of the theory. The rate con formed by applying the fast motional approximation
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 111
(Le., orientational correlation time much shorter than When eq 104 is applied to the thioninelpiodoaniline
the Larmor period or the triplet decay time). Time triplet exciplex decay investigated by Steiner and co
integrating and sample averaging required evaluation workers,lm where the saturation value of the MFE
of Laplace transforms of secondrank tensor time cor amounts to approximately 20% and the parameters
relation functions, yielding a linear matrix equation for correspond to E = 2/3, the results according to eq 104
the timeintegrated, ensembleaverageddensity matrix deviate by up to a factor of 2 from the exact solution.612
from which analytical expressions can be obtained for Pedersen and Freed611treated the tripletmechanism
any observable of interest (after complete triplet decay). CIDEP problem by a numerical method that is quite
Whereas Atkins and Evans were interested in spin po general and applies also to the slowmotional region of
l a r i ~ a t i o n only
, ~ ~ ~recently has their method been the parameters. Their starting equation has been
adapted by Serebrennikov and Minaev612to the prob modified by Steiner and coworkers160by including a
lem of magneticfielddependent product yields. As term for spinsublevelselective triplet decay in order
noted above, this requires introduction of spinsublev to account also for MFEs on product yields:
elselective triplet decay. Serebrennikov and Minaev
b(Q,t) =  w z + W Q ) , d Q , t ) l   1/22[Ks(Q),p(Q,t)l+

used a selective operator of triplet deactivation Ks(Q),
k , p ( ~ , t )  rnp(Q,t) (109)
defined analogously to eq 101103. On the other hand,
the triplet production process and the product forma Here the density matrix p ( Q , t ) is an explicit function
tion from the triplet were assumed to be non sublevel of the set of orientational angles Q , and r nis a Mar
selective. The result obtained for the relative MFD of kovian operator describing the change of orientational
the product quantum yield is612 distribution due to molecular tumbling.623 Triplet
sublevelselective population is accounted for by suit
able initial conditions for the density matrix.
In the case of continuous rotational diffusion, the
Wigner rotational matrix elements Dgb,(Q) are eigen
with T1 given by functions of rn, where, in the special case of isotropic
T1
1
= rotational diffusion, we have
2 4 r&&b,(Q) = D&(L + l)D&b.(Q) (110)
(D2
15kl
+ 3E2)(1 + (:o/kJ2 + 1 + 4 ( 0 ~ / k ~ ) ~ with D, the rotational diffusion coefficient.
3
diffusion coefficient. In this case the procedure yields
the exact result. The quantum yield is obtained from
the kinetic scheme as outlined above. In the special
case where kTxS = kT s, i.e., Ek = 0, the quantum yield
+p of magneticfielddependent product formation from
the triplet is
+ Dk)(kp+
@p = kp(kp + ks  D k / 3 + 6 D r 3 ) / { ( k p
4018) + 2k,,DI3 I(3ks  2Dk)(kp+ Dk + 2D,3)]
(118)
55 1 \ Note that in this review many expressions may differ
from those in the original work because they were
' ~ 4 , s .,IC 2 3 4 5  9 I L <5,a,, adapted in order that they comply with a standardized
e C Abo~ssJ
notation throughout this review.
Figure 45. Results of model calculations775on the triplet As was noted above, the ZFS of the triplet substates
mechanism including sublevelselective depopulation only. Pa has been neglected in deriving the spin autocorrelation
rameters are D, E = 0, ks = 2013, DL = 10, Ek' = 0, and kp = l.
D, is varied as indicated in the figure. values given are absolute function. This precludes of course evaluation of spin
product yields in zero field. Solid lines: results from numerical polarization. However, magnetic field effects on prod
solution of SLE, 109. Data points: results from approximation uct yields from the triplet state are in excellent agree
(USF), given by eq 118. ment with the exact numerical solutions (cf. Figure 45)
if
In order to connect the quantum mechanical spin D , E << k , + k , + 6D, (119)
motion to the kinetic scheme, spin evolution within the
triplet is described in terms of an autocorrelation Comparing this condition with the €condition of Ser
function of the electron spin in the molecular frame, ebrennikov and Minaev,612one can show that condition
developing stochastically as well as coherently due to 119 is compatible with e = 3/2 and has a wider range of
the combined action of rotational diffusion and Larmor applicability than eq 104.
precession of the spin about the external magnetic field. When the ZFS approaches or exceeds the limit of eq
For the case of isotropic rotational diffusion (diffusion 119, this leads to an increase of the Blj2value, since an
constant D , ) and neglecting the ZFS, the probability external magnetic field can decouple the spin motion
p(T,,,tlT,,O) of finding the molecule in a specific sub from the molecular frame only if B 2 D . As may be
state Tat(a' = x , y, z ) a t time t , if it was T, a t time t seen from the numerical solution, however, the limiting
= 0 (with a random orientational distribution, however), highfield magnetic field effect is independent of ZFS,"
is given by and eq 118 again provides an acceptable solution in the
p(T,4T,,O) = highfield limit, even if condition 119 is not obeyed.
y3 + exp(6D1t){l + 2 cos (wet) + 2 cos (2wot)J
Yl5
(113) C. The Radical Pair Mechanism
This function describes an exponential/oscillatory ap 1. Historical Roots
proach to spin equilibrium. The spin motion may be
incorporated into the kinetic reaction scheme by rela Although the development of the radical mechanism
ting it to an equivalent transition rate constant k(T, has been intimately related to the discovery and early
+ T,,):
k ( T , Tar) = 2D,3  (114)
investigations of CIDNP and CIDEP phenomena, it is
worth mentioning that the essential principle of this
mechanism was established about 15 years before by
where D,, is given by physicists in order to explain and evaluate the magnetic
field dependence of positronium Positro
nium, an exotic atom composed of an electron and a
positron, decays in an antiparticle annihilation process,
with p s the Laplace transform of eq 113: whereby two or three photons are emitted, depending
on whether the total spin of positronium is zero (para
4(s + 6D,) form, F = 0) or 1 (ortho form, F = 1). The former
(s + 60,)' + wo2 + process is about 1000 times faster than the latter, so
that the lifetime of the ortho form is correspondingly
4(s + 6D,) longer. Due to the different g factors of electron and
(116) positron (Ag = 4), the m = 0 component of the ortho
(s + 60,)' + 40102 state is strongly coupled to the para state in a magnetic
field, whereby the lifetime of this orthostate component
The best fit to the results of exact numerical solutions is significantly decreased. The quantitative theory of
is obtained by setting static as well as of resonant MFEs was treated in com
s = ko = k , + ks (117) plete analogy to the Ag mechanism in a radical pair of
fixed distance?% Later, the principle of this mechanism
with k s defined by eq 106c. was adapted by Frankevich2MT628 to account for MFEs
In zero field the decay of the autocorrelation function on electronhole recombination (lifetime of Wannier
is purely exponential and D,, equals D,, the rotational excitons) in molecular crystals. However, this work does
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 113
not seem to have had any impact on the development Further, it is of interest that, quite independent of
of the radical pair mechanism in chemical systems. the CIDNP radical pair mechanism, Merrifield and
Nuclear spin polarization in the course of a chemical c o  w o r k e r ~invoked
~ ~ ~ exactly this radical pair mecha
reaction was first seen by Bargon, Fischer, and John nism to explain the magnetic modulation of dyesen
sons and by Ward and L a ~ l e r . ~The ’ effects were first sitized delayed fluorescence in an organic crystal. They
thought to be due to a transfer of spin polarization from provided a quantitative model treatment on the basis
radical electron spin to nuclear spins due to the Over of a stochastic Liouville equation for a radical pair with
hauser mechanism in single radical^.^^^^^^ Soon, how one nuclear spin I = 1/2.
ever, it became clear that special features of the po The radical pair mechanism has been the subject of
larization pattern, e.g., the multiplet effect, could not an appreciable number of review articles (cf. Table 1).
be accounted for by any refinement of the Overhauser Most of them have dealt with applications to CIDNPFl’
mechanism. CIDEP,2°*51 or CIDMP in general.10~1B~23~28~30~35 With the
The basic concept of radical pairs with their corre exception of reviews especially devoted to the primary
lated spin motion as the final cause of electronic and radical pair in photosynthetic reaction center^,^^,^^ re
nuclear spin polarization was suggested independently views of the radical pair mechanism as involved in
by Kaptein and O ~ s t e r h o f Pand ?~~ by~C 1 0 s s . ~Their
~~ magnetic field effects on chemical yields or kinetics
first treatments concentrated on the highfield case, seem to have been a special domain of Russian au
where only STo mixing occurs in radical pairs. t h o r ~ . So~far, ~ the
~ treatise
~ ~ ~by ~Salikhov
~ * et ~ ~ ~ ~
Whereas C 1 0 s s ~ ~ first paper treated ToS tran
in~his gives the most comprehensive account of the subject.
sitions in a radical pair with two nuclear spins I = Of course, in their monograph the theoretical contri
in a noncoherent fashion, characterizing the evolving butions of the authors are particularly emphasized,
nuclear spin polarization as a transverse Overhauser although due credit is given to the work of others.
effect, which brings about equal intensities of emission In this review our prime goal will be to provide a
and absorption within the multiplet of lines, the compact, yet comprehensive, survey of the relevant
treatment by Kaptein and O o s t e r h o f P ~introduced
~~~ theoretical work done so far, compiling and ordering the
the notion of coherent spin motion in a situation where various contributions from a methodological point of
hyperfine coupling energies are comparable to the ex view. We think that providing such a general schematic
change interaction J in a radical pair. Common to both in addition to the more specialized reviews cited above
s ~ g g e s t i o n s was
~ ~ ~the
v ~idea
~ ~ that a sorting of nuclear will be useful for a quick introduction and for more
spin orientations was achieved by the spin selectivity easily assessing novel contributions to the field.
of chemical recombination in the radical pair. This
spinselective cage reaction competes with diffusive 2. General Formalism
separation of the radicals leading to products, which
may differ from those of cage recombination. The role The quantities of interest to the experimentalist are
of gfactor difference in a radical pair for inducing chemical yields Ys(t) and Y T ( t )of recombination
singlettriplet transitions in a magnetic field and products formed in either the singlet or triplet state,
causing net nuclear spin polarization was first demon respectively, or yields of products arising from sca
strated by Gerhart633and by Closs and T r i f ~ n a c . ~ ~venging ~ reactions of the radical Y,(t). These quantities
Finally, the idea that diffusion and geminate reen are identical with or directly related to the yields and
counters of radical pairs are of essential importance was quantum yields in the experimental section. In most
contributed by who treated this problem
in terms of Noyes’ 638 theory of geminate radical pair
reencounter statistics. Thus, a few years after the
 experimental applications only the limiting value for
t m , here symbolized as Ys, YT,and Ysc,is consid
ered. In CIDNP experiments it is necessary to know
discovery of CIDNP phenomena all the essential in Ys,(,)and Ysc,(,),the corresponding product yields as
gredients of the radical pair mechanism had been as signed to the specific nuclear configurations (n). Of
sessed. The rigorous theoretical formalism was devel course, any theory supplying these quantities will be
oped during the 1970s. likewise suitable to obtain Ys, YT, and Ysc character
Consequences of the radical pair mechanism per izing the MARY and RYDMR effects, since these are
taining to the magnetic sensitivity of chemical yields merely the averages of the corresponding quantities
or magnetic isotope effects were fist discussed by Lawler over various nuclear states. Therefore, although CID
and Evans,94and, in fact, the first effect of this kind NP effects in themselves are not the subject of this
was systematically revealed by Molin and c o  ~ o r k e r s l ~ ~ review, theoretical work in this field will necessarily
in systems where CIDNP effects were already known have a bearing on the objectives of it and will be con
to occur.B3 A quantitative analysis of these first effects sidered, too, in this section, as far as the general prob
was already based on the radical pair mechanism.639 lems of the radical pair mechanism are concerned.
In tracing back early theoretical roots of MFEs on The dynamic variables necessary to yield a satisfac
radical reactions, we must mention two other contri tory description of the radical pair kinetics comprise
butions. B r o c k l e h ~ r s considered
t~~~ the implications the electronic (Si) and nuclear spins (Ij),the radical pair
of electron spin relaxation on the MFD of radical pair separation (r),and the relative orientation of the rad
recombination products, mainly with the situation in icals (Q).Whereas the spins have to be treated quan
radioluminescence in mind. Although such mechanisms tum mechanically, radical separation and orientation
turned out to be of minor importance for lowviscosity are usually treated as classical stochastical variables.
homogeneous solution systems, they are of basic im Thus the state of the radical pair is conveniently de
portance for longlived geminate radical pairs, e.g., those scribed by an electronnuclear spin density matrix p
occurring in micellar systems. (r,Q,t). An equation of motion of the spin density
114 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
matrix representing the relevant processes in a radical spin evolution occurs mainly at interradical distances
pair is given in the following generalized stochastic where J may be neglected, the J term is often omitted
Liouville equation (SLE): in explicit treatments of spin motion. Thus we will
p(r,Q,t)= W(r,Q),p(r,Q,t)l + l'(r,Q)dr,Q,t)+ begin with a survey of the work considering constant
Zeeman and hyperfine coupling interactions only.
K(r,Q)dr,Q,t)(120) Having specified the spin Hamiltonian, it is further
Here [ 3 denotes the commutator. The spin Hamilto necessary to define the initial spin state in order to
nian H(r,Q)describes the coherent spin motion of obtain a definite solution for the spin motion. It is
radical pairs separated by r and oriented as specified customary to use the conditional probabilities Tps(t),
by Q. The stochastic operator I'(r,Q) describes the Tp&), Sps(t),and Sp&). Here the left superscript T
random translational and rotational diffusion of the or S denotes the multiplicity in which the radical pair
radical pair. This form of description of the motion of was formed at t = 0 and the right subscript denotes the
quantum systems coupled to a bath via stochastic multiplicity that is probed at time t. Due to the re
classical degrees of freedom has been established and versibility of coherent processes, these will not disturb
justified by K ~ b o . ~ ~ ~ a 1:3 statistical singlet/ triplet mixture of radical pairs.
The electronspindependentchemical change of the From this principle the following relation between the
radical pair is expressed by the last term in eq 120. various probabilities listed can be
Here K (r,Q)represents a general linear superoperator
in electronnuclear spin Liouville space. In general, it 'PT(~) = 1  'ps(t) = 3(Tps(t))= 3(1  T p ~ ( t ) )(122)
may depend on the interradical separation and the Radical pairs originating from random encounters of
relative radical orientations. The operator K ( r , Q )is free radicals (F pairs) correspond to a 1:3 statistical
introduced in a purely phenomenological manner, as are mixture of singlet and triplet pairs. Since their first
rate constants in ordinary chemical kinetics. encounter will usually eliminate more of the singlet
The SLE (120) may be used as a general reference pairs, the radical pairs being left after this event will
point to order the various treatments of the radical pair behave rather like radical pairs with initial triplet spin.
mechanism described in the literature and to assess A more complicated situation concerning the initial
their approximate nature. spin correlation of radical pairs arises when more than
An intuitive approach for handling the problem one electron/hole pair is produced in spurs by energy
stated in eq 120 is to decompose it into the separate rich particle radiation. Here the total spin of a spur is
problems of spin motion and of diffusion and to as zero. However, pair contributions within the spur may
semble their mutual interaction with spindependent have singlet or triplet correlation, the probability of
recombination kinetics in a final step. These aspects which may be obtained from combinatorial analy
will be reviewed separately in the next sections. sis.392i395The problem has been somewhat controver
sia1.393W
3. Spin Motion If the spin Hamiltonian is time independent, it is, in
principle, a straightforward matter to determine the
The various kinds of interactions that have been ex spin motion from the eigenvalues E, and eigenfunctions
plicitly treated in the theory of electron spin motion are 14) of the spin H a m i l t ~ n i a n ~ ~ ~ ~ ~ ~ ~
collected in the following spin Hamiltonian:
Tps(t)= 1/3(1 [1/n(211i + 1)(212k + 111 X
i h
1,25
(a) Exact Solutions of Special Cases. A fairly
general case where explicit closedform expressions have 1 I
been obtained, a radical pair with two arbitrary nuclear
spins Il and I2 with one on each radical, has been solved
by Salikhov et alea5The solution for the more general
case with an arbitrary number of equivalent magnetic
nuclei on each radical may be decomposed into con
tributions of the latter kind.646Correspondingformulas
for the case of two magnetically equivalent sets o f .
protons have been given by B r o ~ k l e h u r s tand
~ ~ ~by
Evans and L a ~ l e r .A~ special
~~ example with nine
equivalent protons on one radical only has been worked
out by F i s ~ h e in r ~the
~ ~analysis of his experimental
results. The model radical pair with one proton on each 0.0 l
radical has been considered in detail by Schulten and
~ o  w o r k e r s . The
~ ~ *simplest
~~ model radical pair with
one nucleus I = 1 / 2 has been used by many authors.
Whereas the case of general fields becomes rather
involved with an increasing number of nuclear spins,
the highfield case can be easily handled for an arbitrary 0.5 
number of spins. This simplification is due to the fact
that nuclear spin quantum numbers are conserved un
der highfield conditions since electronnuclear spin 0.25.
flipflops are not energy conserving in high magnetic
fields. Thus one has to perform only an average over 0
the STo oscillations for the individual nuclear spin 0.01 0.5 1 5 10
states:650 t 
'pT0(t)= [1/IIWli
i.k
+ 1)(21,k+ 1)lC
m
sin2 (w(m)t) Figure 46. Evolution of triplet character in radical pairs produced
with singlet spin ( s p ~ )Solid
. lines: shorttime approximation
~ ~126, with wa = 1 and wL values as indicated
of H a b e r k ~ r n ?eq
(124) in the figure. Dotted lines: zerofield and highfield result cor
with responding to the semiclassical approximation of Schulten and
WolynesB6(eq 129 and 130 with 71 = 72 = 4). In diagram b relative
w(m) = '/,[kl g2)PBBO/ fL + Calimli
i
 Calkmlkl
k
values with reference to the semiclassical zerofield value are
plotted to demonstrate the intermediatefield cases more clearly.
(124a) Note that the time scale is logarithmic.
It is evident that the angular frequency expression 46). The zerofield shorttime behavior is described
reflects the rephasing mechanism of electron spin by 3/16(wat)2, whereas in the highfield case it is
motion. 1 / 1 6 ( W , t ) 2 , indicating that singlet to triplet transitions
A very compact expression for the highfield case with for two of the triplet substates are quenched in high
n X I = 1 / 2 spins only has been derived by Brockle
magnetic fields. The period of time where switching
h ~ r s t : ~ ~ ~
n
of spin motion from lowfield to highfield behavior
SPTo = 1/[1 cos (t(gl  g2)wBBO/h)n cos bkt/211 occurs (cf. also Figure 3 in ref 439) is shifted to earlier
k=l times as the field is increased. This reflects the effect
(125) of the probing time on Bl12observed in several exper
(b) Approximate Solutions for General Fields. iments (cf. ref 158, 307, and 312).
Since the full solution to the problem of spin motion A most remarkable method to approximate spin ev
is rather involved in the general case of many nuclear olution in the general case has been contributed by
spins and an arbitrary magnetic field, resonable ap Schulten and c o  ~ o r k e r s . ~ ~Here @ , ~the
~ ~influence of
proximations that can be handled by limited numerical nuclear spins is approximated by effective classical
effort are desirable. As has been pointed out by Ha magnetic fields resulting from a quasicontinuous dis
b e r k ~ r n it~ is
~ loften sufficient to know the shorttime tribution of nuclear spin orientations. This assumption
behavior of spin motion, for which, on the basis of allows averaging of the nuclear spins, yielding compact
perturbation theory, he was able to derive the following expressions for the zerofield and highfield cases and
expression: series expansions for the intermediatefield case. The
averaged hyperfine contribution of each radical is
+ 2 sin2 ( w ~ t / 2 ) / ( w ~ t / 2 )(126)
' p ~ ( t=) f/16(~at)2[l ~] specified by a characteristic time 7 i , given by
where wL is the Larmor frequency and w, is an average = l/sxaik21ik(1ik+ 1) (128)
k
hyperfine frequency given by
(1) (2) The spinmotion expressions for the zerofield and
+
w, = h1[4/33C4(4 l ) U l , i 2
i
+ "/,CIj(Ij
I
+ l)U2j2]1/2 highfield cases, respectively, are given by
(127) Sp& Bo = 0) =
Equation 126 nicely describes the switching of the spin 7*{1 Yg[1 + 2 C ( t / ~ i ) l [ l+ 2c(t/rz)lI (129)
motion from zerofield to highfield behavior (cf. Figure with
116 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
under conditions of intramicellar diffusion are so far not At zero field T1and T2cannot be distinguished. At
available. higher field Tl processes cause radical pair spin relax
(a) Electron Spin Hopping. During the lifetime of
an electronspin pair the hyperfine environment of each
electron spin may be changed either by chemical
ation between (T+,

T) and (To,S), whereas T2processes
are responsible for To S relaxation. Typical values
of organic radicals in lowviscosity solvents a t room
transformations of the radicals, by which socalled temperature are to be expected in the order of lo6 sl
consecutive radical pairs are obtained (cf., e.g., ref 667 for both TI and T2. (The relaxation times of small
and 668) or by electron hopping between equivalent linear radicals such as OH' with unquenched orbital
molecules, a situation to be considered in systems with momentum may be considerably ~ h o r t e r . ~ ~ ~Thus,
~'"')
high concentrations of electron donors or acceptors. at zero field, paramagnetic relaxation is typically by 23
The effect of such hopping processes is to generate a orders of magnitude slower than coherent spin evolution
random modulation of the hyperfine i n t e r a c t i ~ n It
.~~ processes induced by isotropic hyperfine coupling.
has been theoretically investigated for the highfield
case of CIDEP and CIDNP by Hore and M~Lauchlan~~O
and by Salikhov et al.671t672 For the case of a radical pair
However, if the external magnetic field exceeds the
hyperfine fields, the rate of coherent (T+,T) (To, 
5) processes will fall below that of the Tlprocess. Then
with 1 X I = 1/2 of hfc constant a and electron jumping the MFD of Tl may be reflected in radical pair recom
with a rate constant k between equivalent molecules bination kinetics under suitable conditions, e.g., for long
carrying the magnetic nucleus, the highfield result is732 cage times in micro reactor^.^^^*^^^
The relative contribution of coherent and incoherent
SP T ~ ( ~=) 1/2[1 COS ( & ~ ~ B o t / h ) g ( t ) ] (133) spin motion has been described diagrammatically by
with Brocklehursta7 (cf. Figure 48). Here regions B and C
are the domains of coherent spin motion. The time
g ( t ) = exp(kt/2)[cosh (Rt) + (k/2R) sinh {Rt)] evolution of sps, depicted as an example, corresponds
(133a) to a case with a broad distribution of hyperfine coupling
and constants and may be described by the semiclassical
approximation leading to a limiting value for sps of 1 / 3
R = (k2  a2)/4 (133b) in zero field. In cases with a small number of hyper
In the limit k >> a eq 133 reduces to finecoupled nuclear spins, because of the degeneracy
of several stationary states, the limiting value of sps
' p ~ , ( t=
) 1/[1  exp(a2t/(4k))1 (134) may be higher in zero field than in weak fields where
the degeneracies are lifted (cf. dotted curve in Figure
demonstrating that spin evolution is suppressed if hy 48). In high magnetic fields the limiting value of sps
perfine interactions are averaged over the typical re is 1/2. At low fields the T, = T2relaxation will establish
phasing period. the statistical singlet character of 1 / 4 between regions
The general case of electrons hopping between mol C and D. In higher fields, however, (Zeeman energy
ecules of an arbitrary number of nuclear spins has been larger than hyperfine energy) the transition from the
tackled with the semiclassical formalism developed by hyperfine plateau of sps = 0.5 to the statistical limit of
Schulten and c o  w ~ r k e r s No . ~ ~analytical
~ ~ ~ expressions 'ps = 0.25 will be due to the T, process between regions
have been obtained for the general case but an efficient D and E, the exact position on the time scale depending
numerical method is described. It is shown that with on the strength of the magnetic field. An explicit
increasing hopping rate, the B1l2value first increases, analytical expression for Sps(t)has been derived for the
as is typical for the general situation of lifetime highfield case by Klein and V 0 1 t z ~and ~ ~ by Kubarev
broadening. However, in the region of high hopping et al.:294
rates, the Bl12value decreases toward a limit where the
effect of magnetic nuclei on the exchanging molecules Sps(t)=
averages out to zero. This situation corresponds to the y2(l'I(2~i+ 1)(21j + l))l[C(cos (w,t) exp(2r2t)) +
LJ m
exchangenarrowed limit. (1+ exp(2r1t))/4] (135)
The hopping problem has also been extended to the
case of intramolecular electron hopping between two with w, as defined in eq 124a.
covalently linked donor sites.330i673 Here the hyperfine Equation 135 was derived from a Redfield type
coupling is not averaged to zero in the fast hopping limit equation of motion of the spin density matrix, wherein
but to a finite hyperfine coupling, half as strong as it was assumed that T1 and T2are independent of the
without hopping but with twice the number of nuclear nuclear spin states and do not involve nuclear spin flips.
spins. Klein and used T1only, setting
(e) Paramagnetic Relaxation. The MFD of para rl = r 2 / 2 = 1 / ( 2 ~ , ) (136)
magnetic relaxation times Tl and T2was first discussed
by B r o c k l e h ~ r sas
t ~a~reason
~ for a possible magnetic whereas Kubarev et al.294used
field sensitivity of radical pair recombination kinetics. ri = 1/(2T1) (137a)
Although theoretical magnetic field dependences of T,
and T2have been established for various mechanisms rz = 1/(2T2) (137b)
such as those involving anisotropic g tensor and hy
perfine tensor modulation by molecular tumblingMand From an ad hoc argument F i s ~ h e rarrived ~ ~ ~ at an
spinrotational r e l a x a t i ~ nno
, ~ systematic
~ experimental analogous expression as to eq 135. He used eq 137
studies of the MFD of T1and T2seem to be available together with the assumption Tl= T2,which is justified
in liquid solutions, because ESR measurements are in the case of spinrotational relaxation as the dominant
usually performed at a few fixed frequencies only. mechanism.
118 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
pair recombination by D e u t ~ hand ~ ~by~ Abell and treatments of spin motion and diffusion are applied.
Mozumder.683In these treatments f ( t )was obtained as (a) EXponential Radical Pair Decay. The typical
the diffusive flux into an absorbing boundary a t r = a expression appearing when integrating coherent spin
(Smoluchowski boundary condition) for an initial 6 motion with exponential radical pair decay is
distribution a t r = ro. For neutral radical pairs the 2n2a2r2
result for f ( t ) is457 (l/.r)Jm[sin (nat)12exp(t/.r) dt =
1 + 4n2a2r2
f ( t ) = [Da(ro ~ ) / 2 d / ~ r ~ ( D exp[(ro
t ~ / ~ ) ] ~ ) ~ / 4 D t ] (150)
(145)
Applying, e.g., the spin motion expression for a radical
For radical ion pairs no closedform expression can be pair with one nuclear spin (I= 1/2), the result for the
obtained. The interpretation of the result given by eq integral (149) is10t52
145 as the firstarrival time distribution has been crit
icized by HaberkonP2 and by Razi Naqvi et al.684 sYs(Bo= 0) = 1  3 / s ( a ~ ) ~+[ l UT)^]^ (151a)
Schulten and SchultenM9determined the function f (t )
by solving the Smoluchowski equation with boundary
conditions corresponding to the production of the rad

sYs(Bo m) = 1  ‘/(U7)2[4+ ( ~ 2 7 ) ~ I  l
For a7 << 1 eq 151a,b exhibit a square dependence
(151b)
ical pair at the encounter distance a and to the radiation of the recombination yield on the hyperfine coupling
boundary condition constant. Furthermore, under this condition, the S/T
conversion effect on Y is smaller in a strong magnetic
field than at zero field. The latter feature is reversed,
however, if a7 > 1. This is a peculiarity of radical pairs
where W(r)is the probability density that the radical with few nuclear spins, all localized on one radical. The
pair distance is r. The parameter K has the dimension phenomenon has been analyzed in some detail by
of a linear velocity and determines the total purespin Sarvarov and S a l i k h o ~ .The~ ~ ~anomaly may be at
reaction probability a0of the radical pair tributed to the S/T oscillation amplitude, which is in
= K/(K + D/a) E ~ / a (147) creased by a magnetic field only in the special case of
few nuclear spins on one radical. The oscillation fre
The result for f ( t )is quency behaves uniformly for all hyperfine coupling
f ( t )= K/(TDt)l12[1  cases: It is slowed down in a magnetic field (cf. eq 126).
(b) Diffusional Treatments of Reencounters.
a ( ~ t / D ) ’ /exp(a2t/D)
~ erfc ( c ~ ( t / D ) ~ / (148)
~)] Using the Noyes reencounter function f ( t )(eq 142), one
For radical ion pairs the problem of geminate recom obtains by integrating with coherent spin motion
bination was investigated by numerical integration of terms52
the corresponding Smoluchowski e q u a t i ~ n . ~ ~ ~ ~ Y~ =~ S~m d tf ( t )sin2 (ut)= p/2[1  cos (c) exp(c)]
Razi Naqvi et aLW have compared the model of first 0
reencounter with the diffusional model of radical pair (152)
recombination. According to their analysis, eq 148 with with
K = dv/4 (v is the jump frequency in the random flight
model) yields the correct expression for the first “arrival c = (2m/p)(?rw)’/2 (152a)
probability” whereas expression 145 is an approximation
that may lead to serious errors if the shorttime limit
is of any importance.
Tarasov et a1.559subjected the diffusional model to

Expansion to lowest order in c yields for large p / m
Y(c 0) = c(p/2) = m(7ru)l/2 (153)
the boundary conditions of microscopic spherical re This expression with its characteristic square root de
actors. They determined the coefficients of a series pendence on the singlettriplet oscillation frequency is
expansion for the reencounter probability function f ( t). often used in work referring to the radical pair reen
counter model.
5. Assembling Spin Motion, Diffusion, and An exponential factor may appear in the integrand
Recombination of eq 152, either due to consideration of scavenging
processes on the reencounter probability function or by
So far, most theoretical work on the radical pair consideration of relaxation processes in the spin motion.
mechanism has been concerned with timeintegrated Corresponding results with f = mt3/2have been re
yields Y of radical pair recombination. In many cases ported by Buchachenko and Makarian,679and with the
the function f ( t ) describing diffusion and purespin full Noyes expression (eq 142) by F i s ~ h e or, r ~ using
~~
recombination is combined with spin motion, as de the equivalent Deutch formula, by Kubarev et
scribed by p s ( t ) or pT(t),according to The most general analytical result for an integral of the
type of eq 152 has been obtained by Beljakov and Bu
(149) chachenko6%with the Razi Naqvi reencounter expres
sion modified by a scavenging exponential. The series
A number of representative references, wherein expansion coefficients obtained by Tarasov et a1.559for
methods for assembling various combinations of dif f ( t )in micellar microreactors have been used to obtain
ferent types of spin motion and dynamic probability corresponding expansion coefficients for integrals of the
factors f ( t )have been provided, are compiled in Tahle type of eq 152.
18. There are also included references to other work, Atkinssa9cast the combined problem of solving the
where more advanced methods combining independent diffusional equation for reencounters and performing
120 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
TABLE 18. Theory of t h e Radical Pair Mechanism: Assembling Spin Motion, Diffusion, a n d Recombination
spinmotion
exp Noyes contdiff mutli equiv rate T/Scoupled
year ref f(t) f(t) f(t) reencounter constants diff eq
1969 Kaptein and 0 0 s t e r h o f P . ~ ~ ~ X
1970 Closs et a1.6343675 X
1970/1971 Adrian636,636 X
1971 Lawler and Evansg4 X
Tomkievicz and Cociveraa5 X X
1972 Sagdeev et al.639 X
KapteiP X X
1973 at kin^^^^ X
1973/1974 Buchachenko and M a r k a r i a r ~ ~ ~ ~X t ~
~ X
1975 Sarvarov and SalikhovBa7 Xa X
1976 Haberkorn and MichelBeyerleW X
Schulten et aL302 Xb
1977 AtkinsBag X
HaberkornsE2 X X
Haberk~rn~~l X
Schulten and SchultenM9 X
Werner et aLM3 X
Peder~en~~~
SalikhovasO
1978 Hayashi and N a g a k ~ r a ~ ~ ~ X
Bube et a1."* X
1979 Purtov and SalikhovW Xe
Kubarev et aLZg4 X
Knapp and S ~ h u l t e n ~ ~ ~ X
Schulten and EpsteinG8 X
1980 Purtov and S a l i k h o ~ ~ ~ ~ ~ ~ ~ ~ X
Sterna et a1.577
1981 Tarasov et al.569 Xh
1982/1984 Brocklehur~t~~~~~~ X
1983 Salikhova6
Belyakov and B u c h a ~ h e n k o ~ ~ ~ X
Fis~her~~~ X
1984 Hayashi and N a g a k ~ r a ~ ' ~ X
Knapp and L e r ~ c h ~ ~ ~ XI
1985/1986 Bittl and S ~ h u l t e nBittl
, ~ ~et
~ al.665 Xk
1986 Schulten and Bitt1695 Xk
1987 Baumann et al.441 X Xd
a Here also the case f ( t ) = 1 is considered, yielding the longtime average of p&). bRadial pair dissociation as firstorder rate process in
coupled T / S rate equations. Coupled diffusion equations for 's3RPs with exact spin motion. Summation of operator series. e Combined

with twosite radical pair model. 'Reencounters summed by Monte Carlo path integral calculation. BCoupled diffusion equations for '"RPs
with T S transitions described by rate constants. Boundary conditions corresponding to micellar solubilization of radical pair. 'Monte
Carlo averaging of reencounters based on eq 145. ' f 0: t  3 / 2averaging of spin correlation including twosite electron hopping. kApplying
biradical spin motion, modulated by stochastic variation of exchange interaction (Monte Carlo calculation).
time integration into a compact mathematical form, (c) Summing Up Contributions of Repeated
where the recombination probability is obtained directly Reencounters. Contributions of repeated reencounters
as the Laplace transform of a suitable Green's function to the total recombination yield of the radical pair will
of the diffusion equation. become more important the higher the first reencounter
Several authors have used numerical methods to in probability p and the slower the spin motion. Kap
tegrate eq 138. This turned out to be necessary in cases teid60 was the first to consider repeated reencounters
where diffusion was treated in a Coulombic poten in the case of original triplet radical pairs whereby each
tia1643,649
or where spin motion was too complex, as in reactionless reencounter was treated as a situation
systems with many magnetic nucleiM3or with electron equivalent to the initial production of the triplet pair.
hopping.651 Thus the total recombination yield is just the first
Integration of eq 138 has also been performed with reencounter yield times 1/(1 p ) , which is the sum of
a variable upper time limit, using the simplified ex an infinite geometric series.
pression of eq 148.649Applying the shorttime expan The formalism accounting for the effect of spin
sion of spin motion (eq 126), H a b e r k ~ r n obtained
~~l motion in repeated reencounters was greatly improved
in contributions by P e d e r ~ e nand ~ ~by
~ Salikho~.~~~
Spin evolution between two reencounters is described
by a timeevolution superoperator M which is time
averaged over the distribution of first reencounters f ( t ) .
The total recombination yield summed over all reen
counters where singlet radical pairs react with a prob
ability of X may be written and evaluated as follows:
~  X Q S ) I ~ P ( O )=)
YS= Tr I Q s X [MU
where X is the spinallowed reaction probability per n=O
encounter and S [ x ] is a Fresnel integral. Tr 1QsX[I M I  XQ,)I'P(O)J (155)
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 121
Here p ( 0 ) is the spin density matrix at the instant of matrix by coupled rate equations for the concentrations
radical pair production, and the superoperator &S is of singlet and triplet radical pairs. The first step toward
defined as this end would be to describe the radical pair singlet
triplet conversion by firstorder rate constants km and
QSP = QSPQS (156) kST, respectively. Of course, for coherent processes this
where QS is the normal projection operator onto the must be a rather crude approximation, but it will be
radical pair singlet state. I is the identity operator. appropriate for the relaxational type of spin motion, as
Using the form of eq 145 for f ( t )and considering only has been applied, e.g., by Hayashi and N a g a k ~ r to a~~~
coherent ToS transitions, P e d e r ~ e derived
n ~ ~ ~ closed the problem of intramicellar radical pair recombination
form expressions for Ys under different initial condi kinetics. There have been also attempts to correlate
tions (To,S, or F pairs). Furthermore, he could show coherent spin motions with rate constants, using the
that, independent of the particular form of f ( t ) , the following expression establishing a suitable correlation
results can be expressed in terms of two basic quanti with the reencounter model:
ties, A and F*, only. These are defined as
A = ’Ys(w = 0) = X / ( 1  p + P A ) (157)
where p is the probability of at least one reencounter This type of relation has been used by Tomkiewicz and
(cf. eq 143), and C o c i ~ e r aapplying
~ ~ ~ the exponential form of f ( t ) and
P ( w ) = TOYs(X = 1, w ) (158) by Bube et al.l12 with the Noyes reencounter function
(eq 141, using 7 = 7 D = a 2 / D ) .
Here w is the frequency of ToS transitions. Actually, spin motion can be strictly separated from
The quantities A and F* have the meaning of a total diffusion and recombination only if triplet and singlet
recombination probability of singlet pairs if spin evo radical pairs have identical recombination probabilities.
lution is excluded (A) and the total recombination Spatial inhomogeneities in singlet and triplet pair dis
probability of initial To radical pairs if every singlet tribution arise, however, at the reaction zone when re
reencounter leads to recombination (F*). With these combination rates are spin dependent. The reencounter
quantities the following relations hold, independent of model represents a convenient basis for taking different
the particular diffusion model applied to describe reactivities of singlet and triplet radical pairs into ac
reencounters: count. The spin motion on each diffusional trajectory
= AF*/[l + F*(l  A)] (159a) between two reencounters begins with a spin situation
originating from the last encounter. A suitable way to
incorporate this into the formalism is the operator
‘Ys(X,w) = A i l  F”(1 A)/[l + F*(l  A)]) (159b) power series outlined above. However, whereas this
method can easily provide the overall recombination
F Y s ( X , ~=) (A/2)(1 + AF*/[l + F*(l  A)]) (159~) yield, it cannot adequately describe the explicit time
Setting dependence of the recombination yield, since at a given
instant of time there are simultaneous contributions of
ToYs(X,w>= 3(TYs(X,w)) (160) different orders of reencounters.
Without abandoning the treatment of spin motion as
one can derive an independent process, the realtime recombination
‘YS(X,W) = A  3(1  A ) ( T Y s ( X , ~ ) ) (161) kinetics for different reactivities of singlet and triplet
radical pairs has been described by coupled rate equa
a general relation between total singlet recombination tions in several papers by Schulten and cowork
yield of initial singlet and triplet radical pairs that has e r ~ . Within ~ ~the~exponential
~ ~ ~ model * ~of dissocia
~ ~
been obtained by S a l i k h ~ on v ~the
~ ~basis of a kinetic tion these rate equations are as follows:
interpretation of thermodynamic equilibrium.
The reencounter operator formalism has been ex CS = (CS + CT)(’~T)  (ks + kesJCs (163a)
tensively applied by Salikhov and coworkers,680who
obtained closedform expressions for the recombination CT = (CS + cT)(s@T)  (kT + kesc)CT (163b)
yields of singlet, triplet, and F pairs, considering the
combined influence of anisotropic reactivity and rota Here c s ( t ) and c T ( ~ )are the concentrations of singlet
tional diffusion,6wusing semiclassical models of spin and triplet radical pairs, respectively. The quantity SpT,
motion652and model radical pairs where spin motion the time derivative of spT obtained from separately
may be conveniently described in zero field646and solving the spin evolution problem, is an effective rate
general fields.658 “constant” of S / T transitions. The approximation in
Schulten and Epstein68considered radical pair reen herent in eq 163a,b is the assumption that the rate of
counters in the context of a pathintegral method with spin evolution should be in effect independent of the
numerical Monte Carlo simulation of radical pair dif cS/cT ratio although this will deviate from the pS/pT
fusion trajectories. Baumann et a1.441 applied the ratio of pure spin motion if ks and kT are different.
multireencounter formalism using an exponential The concept underlying eq 163a,b has been also ap
reencounter probability function for radical pairs in plied with the continuous diffusion model, whereby the
water nanodroplets in w/o microemulsions. equations turn into partial differential equations for
(d) Use of SpinMotionEquivalent Rate Con cs(t,r) and cT(t,r). The rate constant Iz,, is replaced by
stants and Master Equations. It would appear con a diffusion operator with suitable boundary conditions,
venient from the chemist’s point of view to approximate and ks and k T become rdependent “optical
the stochastic Liouville equation for the spin density potentials”.643The solutions of equations 163a,b and
122 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
their continuousdiffusion counterparts have been ob neous treatment of spin motion and recombination is
tained by numerical integration. The results for the to consider a model with the radical pair fixed at a
diffusional model compare favorably with those ob certain distance where recombination and dissociation
tained from numerical integration of the full SLE.643 compete as firstorder rate processes (the socalled
Coupled diffusional equations for cs and CT have also “exponential” Such a model may be physi
been applied by Sterna et al.577to model the magnetic cally realistic under solidstatelike conditions, e.g., for
isotope effect a t zero field, however with the cruder radical pairs produced in photosynthetic reaction cen
approximation of actually timeindependent rate con ters (cf. ref 511,532534,707, and 709). However, they
stants for singlettriplet conversions. The boundary have been also applied to describe the situation for
conditions considered by these authors were chosen so b i r a d i c a l or
~ ~radical
~ ~ ~ pairs
~ ~ ~in liquid solutions (cf.
as to apply for geminate recombination in homogeneous ref 157, 671, 699, 704, 706, and 708).
solutions and in micelles. A typical form of the onesite radical pair SLE with
different rates of singlet and triplet recombination is
6. Treatments Based on Direct Solutions of given by1579302
Stochastic Liouville €quations
P = i[H,Pl  ~ D 
P ( k s / i ) [ Q s , ~ I + ( ~ T / ~ ) [ & T , P I +
The necessity of treating spin motion and recombi (167)
nation together arises when singlet and triplet pairs In Table 19 are listed a number of references where
recombine with different rate constants. As has been such types of equations or their twosite extensions are
analyzed in some detail by Schulten et aL302and by treated. The table provides a shorthand survey of
Haberkorn and M i ~ h e l  B e y e r l esinglettriplet
,~~~ tran several characteristic features of these treatments (for
sitions are slowed down if singlet and triplet levels of other examples, including the effect of microwave fields
the radical pair are differently broadened by spinse in the spin Hamiltonian, see below (RYDMR section)).
lective rate processes. The appropriate method for a Most solutions have been worked out for overall re
combined treatment of spin motion and spindependent combination yields only. These are obtained according
reaction kinetics is to use statistical Liouville equations. to
Density matrix equations of motion have long been
used to describe combined coherent and incoherent
) J m Q s ( n ) ~ ( t )dt = ~ s ( TTr
Ys(T) = ~ s ( T Tr ) {QS(T)/~~
processes in magnetic resonance.6m98 Thus it was only
necessary also to incorporate the kinetic effect of dis (168)
sociation and spinselective recombination of para
so that it is only necessary to determine the timein
magnetic particle pairs. Two forms of the spinselective
tegrated density matrix /j. Time integrating eq 167
recombination term have been suggested. For selective
yields a system of linear equations that are of the type
singlet pair recombination they read as follows:
of the Liapunov matrix equation:533
KSP= ks / 2 [Qs,pl+ = ks/ 2 (QsP+PQs) (164a)
Bp + pB+ = p ( 0 ) (169)
KSP= ksQs~Qs (164b) for which efficient numerical solution procedures have
Here ks is the chemical rate constant for singlet pairs been reported.710
and Qs the projection operator, projecting onto the The conservation of the z component (parallel to Bo)
radical pair singlet spin subspace. of the total spin and, in case of zero field, also the
The anticommutator (eq 164a) was introduced by conservation of the absolute value of total spin allows
Johnson and M e r ~ i f i e l dto
~ ~describe spinselective decomposition of the coupled system of equations (eq
triplettriplet annihilation and has been adopted for 169) into several systems of reduced dimension. How
spindependent radical pair reactions in CIDNP theory ever, for the generalfield case, analytical solutions still
by Tomkiewicz et al.699and by Evans et al.700 The have been obtained for radical pairs with one nuclear
second form (eq 164b) has been advocated by Pedersen spin (I= l / J only (cf. Table 19). In the zerofield case
and Freed.701 Both forms conserve the Hermitian a general compact analytical solution has been obtained
property of the density matrix. However, as has been for an arbitrary number of nuclear spins I, where all
shown by Haberkorn702the second form (eq 164b) may have the same coupling constant.709
lead to physically meaningless results for the density A general perturbational solution, both, stationary
matrix (negative occupation numbers of quantum and time dependent, has been derived by Lendia705He
states). A linear combination of the form considered a SLE in the form
KSP= ki/2[Qs,pl+ + k z Q s ~ Q s (165) p = (i[Ho,p] + L o p ) + (i[H,,p] + LIP) + B =
Pp + Qp + B (170)
may be used, however, without such problems,702if the
following condition is obeyed: where the terms in the first parentheses define the
unperturbed part, those in the second ones contain the
k, 2 lz, 2 0 (166) perturbation, and the operator B describes the contin
Expression 165 takes into account spinexchange pro uous production of radical pairs. The stochastic su
cesses in the radical pair, which lead to singlettriplet peroperator L o must be diagonal in the basis diago
phase randomization. When this expression is used, the nalizing Ho in the sense that
effective recombination rate constant for singlet radical (LO)&= 8liSmklik (171)
pairs is (k,  kz).
(a) SLEs for Discrete Radical Pair Sites (Expo The solution up to second order is provided in terms
nential SLEs). The simplest approach to a simulta of the matrix elements of the superoperators P and Q .
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989,Vol. 89,No. 1 123
TABLE 19. Theory of Radical Pair Mechanism: Applications of Exponential Stochastic Liouville Equations
no. of nuclear spins other magnetic type of
year ref sites IlJ2 interactions" field solutionb remarks
1972 Groff et al.& 1 var A C
Tomkiewicz et al.689 1 m A d
1974 Groff et al.m 1 J,D var A' C
Atkins and Evans709 2 J vag A d
1976 MichelBeyerle et al.167 1 0, A
var N
Schulten et al.302 1 m A P
1977 Sar~arov~~ 1 relax# A
LendiIo6 1 h var P h' P
1978 Werner et 2 s' var N I
Schulten et a1.622 2 var' A' m
1979 Haberkorn and Mi~helBeyerle~~~ 1 J 0, A i
var N
Haberkorn et al.6a 2 s' n i
Miiller et a1.1T6 20 S var A C
1980 Kubarev and S h ~ s t o v ~ ~ 2 s m A
1982 Salikhov and Sarvaro@I1 nq m A d
N
Papier et alaa7 39.'
1 s var A C
Tang and Norris707 J,D var NP i
1982 Boxer et aLM6 1 J,D varbb A aa
1983 Salikhov and Mikhailov7" 2 J 0 A
1984 Stich et a1." 1 J var P U
Hoff and H ~ r e ~ ~ 1 s' N 19 v
1985 Chidsey et a1.6I1 2CC W W A 19 w
1986 Schulten and WindemuthsZ3 2 V d A' m
1987 Goldstein and 2cc 0 N j,
varbb A
" J, exchange interaction; D, electronspin dipolar interaction. A, analytical, exact closed form; P, perturbational; N, numerical.
Application to sensitized hole injection in crystals. CIDNP application. e kS = kT f Only SIT coupling considered. 8 T1and T2relaxation
in one radical. ,+Generaloperator formalism. Exchange interaction with third radical included. 'Application to photosynthetic reaction
centers. Anisotropic hfc included. 'Evaluation of orientational dependence. Model for biomagnetic sensory mechanism.
Transformation to effective onesite radical pair SLE. Second site corresponds to free 2D diffusion. P Also with timedependent solution.
qTo simulate electron hopping. 'Third site corresponds to diffusing hole trapped on surface. #Variable electric field affects escape time of
hole from surface to volume of crystal. With averaging over discrete Gaussian distribution of hfc constants. "Biradical in the gas phase.
" Calculation of electron spin polarization. Derivation of general relation between 3P decay rate and yield; cf. text. Applies to general
nuclear spin state, since this is a constant of motion under highfield conditions. YSemiclassical approach; B A and BBare effective hyperfine
fields at radicals A and B. 'Generation of nuclear spin polarization and kinetic effects derived from it. Oa Accounting for anisotropic
interactions and performing angular average. bbP+*I* and 3P I. "Variable field, but only in the highfield limit.
Lendi's formalism has been applied by Stich et a1." describing transitions between the different radical pair
to analyze a MFE on a biradical decay in the gas phase. sites. Atkins and Evens703treated the CIDNP problem
They considered a onenucleus (I= 1/2) model radical in biradicals using a twosite exponential model.
pair with Hoand L o given by However, even this twosite model turned out to be not
really sufficient to account for the dynamics of dis
Ho = gPBBoWi + 5 2 )  J('/z + 25152) (172) tancedependent exchange interaction in such systems
(cf. ref 346 and 695).
Exponential SLE models have been widely applied
The perturbational terms were for the analysis of magnetic field effects in photosyn
thetic reaction centers (cf. also the review by Boxer et
HI = aSJ1 (174a) al.45). Most of these treatments have taken exchange
L, = 0 (174b) interaction into account. As an example of an exact
analytical solution to eq 167, with kD = 0 and H given
Stich et a l . I B have determined the parameters J , ks, and by the sum of eq 172 and 174a (i.e., for one nuclear spin
kT by comparing the perturbational solution with ex with I = 1/2 and hfc constant a), we quote the result of
periment. It is, however, doubtful whether the simple Haberkorn and MichelBeyerlem3for the zerofield and
onesite model can satisfactorily account for the fluc highfield cases (in the original paper  2 J is used in
tuations of the exchange interaction caused by the place of J in eq 172; eq 175a is adapted correspond
random motion of the biradical endtoend distance. ingly):
For internally mobile radicals and freely diffusing
radicals in solution the onesite exponential model is 'YT(B0 = 0) = 3a2kT(ks+ kT)/([3a2 + 4kskT] x
certainly not adequate since it has turned out that spin ~ + ~ / 2 ) ~(175a)
( k s + k ~ + )16ksk~(2J )
motion occurs essentially at separations where recom
bination is not yet feasible. Therefore, in order to keep
the advantage of the mathematical simplicity of the
'YT(&  a) = U2kT(ks + kT)/([U2 + 4 k s k ~ ]x
(ks + kTl2 + 1 6 k s k ~ ( 2 J ) (175b)
~)
exponential model, radical pair models with two sites
or more than two sites have been intro A generalization of eq 175b accounting also for an
d ~ ~ e dwith ~firstorder
~ ~rate processes
~ ~ ~ isotropic
~ ~hyperfine
~ ~and Zeeman
~ ~ interaction
~ ~ and~ for * ~ ~
124 Chemical Reviews, 1989, Vol. 89, No. 1 Stainer and Ulrich
dipolar electron spinspin interaction has been derived more distant to the special pair. This model was dis
by Boxer and c o  w o r k e r ~ . In
~ ,this
~ ~ case the hyperfine cussed as a possibility to reconcile the fast rate of for
coupling constant a in eq 175b is replaced by an ef ward electron transfer with the rather low value of the
fective coupling constant w. The corresponding relation exchange energy J evaluated from the magnetic field
was further generalized to account also for the situation dependence of sYT. Such a discrepancy arises if it is
of a radical pair with many nuclear spins by integrating
the yield sYT over a Gaussian distribution of the ef
fective coupling constant w. It must be emphasized that
transfer ('P*I 
assumed that the matrix element for forward electron
P'I) and the exchange energy in the
radical pair originate by pure throughspace interac
averaging over independent nuclear states is a rigorous tions. Meanwhile, experimental evidence has been
approach in the highfield limit. obtained515pointing to the important role of superex
Results for intermediate fields have been obtained change, whereby the energy of virtual orbitals of in
only numerically. They have been used to analyze in tervening molecules comes into play. This yields dif
detail the influence of parameters J,a, ks, and kT on ferent values for the relevant exchange integrals in the
the behavior of a photosynthetic reaction center radical radical pair and in the matrix element of forward
pair. The MFD shows case 1 type behavior, and B1/2 electron transfer. Thus the model of Haberkorn et al.534
is approximately determined by the largest of the four seems to have become obsolete. However, the theo
parameters. Equations 175a,b are easily adapted to the retical method for treating the twosite radical pair
case k D # 0 by substituting (ks + kD) for ks and (kT + model is still of interest. It was shown that the coupled
k ~ for ) k T and by multiplying the yields by k ~ / ( + k ~ stochastic Liouville equations for RPc and RPD in their
k D ) . In this way the equivalence of eq 175a (zerofield timeintegrated forms may be transformed to an ef
case) with a corresponding result obtained by Salikhov fective onesite SLE which allows reinterpretation of
~ ~general values of nuclear spin I can
and M i k h a i l o ~for the parameters J , ks,and kT in terms of the parameters
be demonstrated. J , ks, and kT of the close radical pair and of the tran
Werner et al.532considered a more realistic model of sition rate constants for interconversion between the
the reaction center radical pair (cf. scheme 64 and two radical pair sites.
Figure 39) where paramagnetic exchange between the A remarkable extension of the twosite radical pair
intermediate radical 1' and the prereduced primary model has been developed by Charli?, Willig, and co
acceptor radical X' is taken into account using the spin w o r k e r ~for~ the
~ ~ situation of dyesensitized hole in
Hamiltonian jection into molecular crystals. Here site 1of the radical
H = gpBBO(S1 + S2 + S 3 ) + aiS111 + ~2S212 pair is a socalled bound pair of an electron, localized
at the semireduced adsorbed sensitizer, and an electron
Jp1(72 + 25152)  JI& + 25253) (176) hole in an adjacent molecule of the crystal. Firstorder
Furthermore, the primary electrontransfer step with ("exponential") dissociation of the site1 radical pair
the singlet excited special pair lP* is considered to be yields the site2 radical pair, where the hole undergoes
reversible (cf. Figure 39) and is formally treated by a twodimensional diffusion along the surface, since its
twosite radical pair model. The first site corresponds image charge in the surrounding electrolyte prevents
to 'P*, where J is large and S / T phase randomization fast escape into the volume of the crystal, also described
occurs. The second site is the true radical pair site by a firstorder rate process. Spin motion occurs mainly
2P2+I(with spin Hamiltonian (176))where S/T mixing in the site2 situation, i.e., during the twodimensional
takes place. The model has been analyzed by detailed diffusion of the hole, where it is described by a spin
numerical calculations for two nuclear spins I = 1/27 one evolution superoperator M ( t  t'). Returning to site
each at P and I. 1 is described by a reencounter function f ( t  t')
Reversible formation of the special pair triplet state adapted to twodimensional diffusion and containing
3P from the radical pair P*+I'has been theoretically an exponential factor for the escape process into the
analyzed by Chidsey et al.,511who established a general volume of the crystal (rate constant ka. The combined
relation between the observed rate constant of triplet
decay kobd, the rate constant kIsc of the process 3P
lP0, and the yield of triplet formation sYT from the
 spin evolution reencounter superoperator thus becomes
E ( t  t ' ) = M(t  t ' ) f ( t  t ' ) (178)
radical pair obtained in the purely irreversible case: The density matrix equation of motion of site1 radical
kobsd = kIsc + &!(sYT) exp(M/kT) (177a) pairs assumes the form of an integrodifferential equa
tion:
Here AH is the enthalpy difference between triplet and t
radical pair. Recently eq 177a has been generalized by p = Ain$ + k  J 0 E(t  t ' ) p ( t ' ) dt' (179)
Goldstein and to include the case where the
radical pair P ' T may undergo further electron transfer Lint is the Liouville superoperator describing spin
to an adjacent quinone (P'+I'Q ,P'+IQ') with a rate motion and kinetics of the radical pair in site 1,which
constant kQ: decays into site 2 with a rate constant of k. Laplace
transforming and letting s ,0 yields
p ( 0 ) =  Lin$  kEz (180)
a matrix equation that may be solved by standard
methods. The elements of the superoperator E are
given by
Haberkorn et a1.534distinguished. two sites of the in
termediate electron acceptor I, one closer and the other
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, NO. 1 125
where umnare the freqyency eigenvalues of the site2 and neutral donor and/or acceptor molecules has been
spin Hamiltonian and f ( s ) is the Laplace transform of treated by Salikhov and S a r ~ a r o v for ~ ~ the
l highfield
the reencounter function f ( t) for twodimensional dif limit @/To mixing only) using an nsite exponential
fusion. SLE model. In one radical pair site nuclear spin states
The method is actually a combination of the expo are conserved in high magnetic fields; however, on
nential SLE with the assembling method of the last electron hopping the radical pair may find itself in a
section. It has been extended to include also a third, different nuclear spin state. Thus each nuclear spin
discrete site, where the twodimensional diffusion of the state may be considered as a separate radical pair site.
hole is interrupted by being fixed for a while in a .The semiclassicaltreatment of hyperfine coupling has
shallow surface trap.467 been combined with the stochastic Liouville formalism
The exponential SLE has been used in several cases by Goldstein and Here the nuclear spin states
to study anisotropic interactions in photosynthetic re are assumed to be unchanged during electron spin
action centers, e.g., electron spin dipolar i n t e r a c t i ~ n ~ ~ ,motion,
~ ~ ~ which is strictly valid only in the highfield
or g tensor and hyperfine tensor anisotropies.505 limit. The nuclear states are represented by equivalent
Schulten and used a twosite radical effective magnetic fields in each radical. For each fixed
pair model with one nuclear spin (I= 1/2) in order to pair of hyperfine fields (BA,BB) on radicals A and B the
assess the influence of magnetic anisotropy of hyperfine SLE is solved according to the method of Haberkorn
coupling in oriented systems. It was found that even and M i ~ h e l  B e y e r l e .The
~ ~ ~solutions depend on the
in the earth’s magnetic field resonable angular depen S / T mixing frequency
dences of product yields would ensue so that the model
could be discussed as the basis for a biometric sensory = gl*BIBA  BBl/h
mechanism for living organisms finding their direction
with the help of the earth’s magnetic field. Hoff and and are averaged over the various distributions R(u).
Lous514suggested that anisotropic electron spinspin The work focuses attention especially on the production
interaction might be considered as a potential principle and consequences of nuclear spin polarization (ex
for biomagnetic sensing. pressed in the particular form of R ( o ) )in photosyn
As mentioned above, in prereduced photosynthetic thetic reaction centers. Two mechanisms of such nu
reaction centers paramagnetic exchange between the clear spin polarization are pointed out:
radical pair P’+I’ and X’ is of importance for the (a) Under singleexcitation conditions sorting of nu
magnetic field dependence of triplet formation, but also clear spin states in the branching of the radical pair
in spin polarization of the prereduced primary acceptor. ‘(P*+I*) to form PI and 3PI leads to differential nuclear
This has been theoretically investigated in some detail spin polarization of PI and 3PI. If 3PI decays to PI,
by Hoff and Hore709using the exponential SLE for however, prior to nuclear spin relaxation, net polariza
malism. tion will be zero.
The effect of paramagnetic exchange with a nearby (b) Under stationary irradiation conditions the faster
doublet state has been also considered in a twosite nuclear spin relaxation in the paramagnetic 3PI state
model by Kubarev and S h ~ s t o v According .~~ to their leads to a stationary nuclear polarization of PI. This
reasoning, the effect of paramagnetic exchange on the polarization causes an appreciable effect on the satu
yield of escape may be much larger than in the most ration value of [3PI] as a function of pump light in
favorable case of the Ag mechanism in a onesite pair. tensity. A decrease of nuclear polarization by resonant
This could facilitate the detection of “latent” radical RF absorption is predicted to give rise to significant
pairs in biological systems. effects on reaction yields and kinetic parameters, thus
The influence of paramagnetic relaxation on singlet enabling “RYDNMR”type experiments to be per
and triplet recombination yields of radical pairs has formed.
been modeled by Sarvarov704in the framework of the (b) Stochastic Liouville Equations with Contin
onesite exponential SLE. For the case that spin re uous Diffusion. In this section we will deal with
laxation is only efficient in one of the radicals, analytical publications where methods of direct solutions of the
expressions have been obtained as follows: full SLE in the form given in eq 120 are described.
Here translational and rotational diffusion of the rad
SYS = icals are modeled by a stochastic operator I’(r,Q),which
(kSrc/4A)[4 + 3 r c / T 1 ~+ 27c/T2A + r c 2 / T 1 A T 2 A 1 is usually restricted to configuration space; i.e., it is
(182a) assumed that relaxation times of linear and angular
molecular momentum are infinitely short. This type
TYS = ( ~ S T C / ~ A ) [ T C /+~ T~ ~T AC / ~ T+~ ‘;/TlAT2AI
A of stochastic motion is tantamount to assuming the
(182b) socalled sudden perturbation limit of timedependent
quantum theory. As a consequence, SLEs with this
with term would not be adequate to describe slow passage
A = (1 Ir c / T i ~ ) (+l T,/T~A) of radical pairs through domains where the energy ei
ksTc(l + 3Tc/4T1~+ TC/2T2, + T ? / ~ T ~ A T(182~) ~A) genstate basis changes. In such cases quantum theory
would predict adiabatic changes of quantum states. In
ks is the rate constant of singlet pair recombination, r, order that eq 120 is applicable, the condition for a
is the mean cage time, and T 1 A and T2Aare the re sudden crossing from the region where hyperfine cou
spective relaxation times of one of the radicals in the pling determines the eigenstates of the spin Hamilto
pair considered to have a particularly short spin re nian to the region where they are defined by exchange
laxation, e.g., small inorganic radicals. interaction must be fulfilled. In simplified form this
The problem of electron hopping between radical ions condition may be stated as
126 Chemical Reviews, 1989, Vol. 89,NO. 1 Steiner and Ulrich
TABLE 20. Theory of the Radical Pair Mechanism: Applications of SLEs with Continuous Diffusion
SIT exchange magnetic max order of diffusion boundary method of
year ref coupling" interactionb field DM blocks' potentiald conditionse solutionf remarks'
1972, 1973 Pedersen and Freed711z712 m 2 0 Ar
1973 Pedersen and Freed7O' m 2 J Ar
Evans et al.700 m 2 0 A
1974 Pedersen and Freed713 m 2 c, J Ar
1975 Pedersen and Freed7I4 m 2 Hj Ar
Evans and L a w l e P var 3 0 AE
Salikhov et al?15 m 2 0 A
1976 Evans716 m 2 0 A
Sarvarov and Salikhov717 var 2 0 A
'I2 3 N
1977 Werner et aLM3 '/2!'/2 J" var 6 C Ar, At
Haberkornw2 P 6 var P 0 AE
Haberkorn"' P 6 var P 0 AE(t)
1977, 1978 de Kanter et al.a6171g720 'i%R e var 8 P" Ar
1979, 1980 Adrian and M o n ~ h i c k ~ 'I2 ~~,~~~ e var 2' 0 AE
1979 Zientara and Freed724 'I2 e var 3 0 Ar
Zientara and Freed725 WN e, et m 2 0 Ar, 8"
1982 Sh~shin~~~ WN e' m 2 C" AP
Sarvarov et a1.668 WN W m 2 0 A
1984 Mints and P ~ k h o v ~ ~ ~ Ag, R" 0 var 2.Y 0 A
1985 Luders and S a l i k h o ~ ~ ~ ~Ag 0 var 2 0 A
1986 Shushin7" P P var P C AP
OWN, S/To coupling with fixed nuclear spin states; R, paramagnetic relaxation; Ag, Zeeman coupling of S and To;figures refer to nuclear
spins present. be, Jo exp(ar); 6, 6(r  a ) (a is the reaction diameter). cBlock diagonalization of p in selectionruleadapted basis. dC,
Coulombic potential; J , exchange interaction included in diffusion operator. e sp, specular boundary condition; rd, spinselective radiation
boundary condition at r = a (a is the reaction diameter). f a r , A t , finite differences; A, analytical; N, numerical; AE, analytical method,
affording result in a closedform expression; AP, analytical, perturbational approach. g CIDEP calculations. Reflecting walls at r = 0 and

r = a, &type rdependent singlet reaction at r = a, 'CIDNP calculations. jH,hydrodynamic effects, applying Oseen's tensor. kConsecutive
radical pair. 'Reflection at 0 < b I a. "'Treatment of homogeneous radical recombination, boundary condition at infinity p(r m) = U A X
uB. "Polymer chain dynamics, biradical. 'Various step models for distance dependence of J. PGeneral theory. qGenera1 timedependent
theory. 'S/T* mixing only. *Unless otherwise stated (CIDNP, CIDEP), radical recombination yields are calculated. 'Angular dependence
of exchange interaction described by a cos 0 term. "Orthogonal expansion in Legendre polynomials. "Exponential J ( r ) without Coulombic
interaction or Coulombic interaction with 'hardsphere" type exchange interaction. Radiation boundary condition for pm, absorbing
boundary condition for psTo, specular boundary condition for pTiT,. " &dependent Tl and 7'2 relaxation times. ?Explicitly included pss, p s ~ ~ ,
pT@! ~ T ~ ~TT +~ T,+and
, pTT. Boundary conditions appropriate for micelles: spinselective radiation boundary condition at rmin= a, general
radiation boundary condition for escape at rm=. In the finitedifference methods spinselective reaction is added as an independent
firstorder process in certain Ar increments.
creation of a singlet, a triplet, or a diffusional (F) radical be imposed on the radical pair models. A disadvantage
pair, respectively. is that the parameter dependence of the results has to
The two types of boundary conditions used for the be cast in numerical tables. Using, however, dimen
diffusion operator are specular (sp) and radiative (rd) sionless parameters a fairly comprehensive survey of the
conditions given by eq 187 and 188, respectively. various cases could be established.18 Although the work
of Pedersen and Freed is mainly devoted to a calcula
= 0 (specular boundary condition) tion of CIDEP and CIDNP effects, the parameters F
and A, which may be combined to obtain the general
(187) recombination yield under the condition of spin motion
and spindependent recombination probability (cf.
section 5 ) , are most valuable for those interested in
D( $) ra
= K ( a ) p (radiation boundary condition) magnetic field effects on chemical yields.52
In the finitedifference approximation the distance
(188) domain from rmh,generally the radical pair encounter
distance, to some rm, is divided into discrete Ar in
With specular boundary conditions the number of crements whereby, without loss of accuracy, great im
radical pairs is conserved, so that radical recombination provements in computer storage and time savings can
has to be described by a separate term. Several au be achieved if the length of Ar is increased in a geo
J " Oused condition (187) a t rmin= 0 and
t h o r ~ ~ @ ~have
metric progression toward the upper limit of the r
introduced a reactive sink at r = a, corresponding to the range.724Introducing r discretization, the SLE is turned
encounter radius. Evans7I6 has shown that mathe into a system of linear equations for the matrix ele
matical admission of distances r C a, which is physically ments Pkr(ri,s).A critical discussion of the convergence
impossible, does not influence the results too drastically.
limits with respect to parameters Ar, rmm,and Laplace
The consequences of representing the exchange inter transform variable s has been given in a review by Freed
action as a &function are more serious, but this aspect
and Pedersen.18
is more important in CIDNP effects than in chemical The dimension of the linear matrix equation to be
yield effects. Specular boundary conditions are usually
solved is determined by the coupling scheme of the p
applied in connection with finitedifference approxi matrix elements. In the highfield limit there is only
mation methods, whereas the radiation boundary con
dition is usually applied in connection with analytical
To/Smixing and a conservation of nuclear spin states.
The complete problem is decomposed into a number
solutions of the continuousdiffusion SLE. Since the of 2 X 2 spin matrix elements multiplied by the number
superoperator K represents the effect of spindependent of Ar increments. In the lowfield case all electronic
recombination, not all matrix elements of p are equally spin states are coupled and nuclear spin states, too, are
affected. In the case of exclusive singlet recombination, not conserved. Thus the dimension of coupled blocks
eq 188 is tantamount to a reflecting boundary condition of the density matrix rapidly increases with the number
for pT,T,, whereas it corresponds to an absorbing of nuclear spins and only rather simple model spin
boundary condition for pss and pST (if recombination

of singlet radical pairs is diffusion controlled). In the
limit r m the specular boundary condition is usually
employed. However, in the finitedifference meth
systems have been s t ~ d i e d . ~ ~ ~ 7 ~ ~ ~ J ~ ~
Using the finite difference numerical integration
method Pedersen and Freed investigated in detail the
influence of spatial extent of the exchange interaction.712
0 d s , ~ ~which ~ ~have ~ to
, be
~ terminated
~ ~ 1 ~at~some ~ r
This turned out to be especially important when dealing
= r, an absorbing boundary condition
with CIDEP effects. On the other hand, it has been
p(rm,, t ) = 0 (absorbing boundary condition) shown by a number of workers that for CIDNP and
(189) reactionyielddetected magnetic field effects, the spe
cial form of exchange interaction is less important.643@2
is customary.
The reason for this significant difference is that, in
In the case of radical pairs in micelles it is appropriate order to produce CIDEP weak exchange collisions must
to use the radiation boundary condition at r = r,,
corresponding to the micellar occur in the radical pair637,which is more likely with
a farreaching, fairly slowly decaying, exchange inter
The SLE approach has also been applied to describe action.
homogeneous recombination of radicals,717in which case
the suitable boundary condition at infinity is given by Other aspects that have been studied concern the role
of exchange and Coulombic forces as they modify the
lim p ( r , t ) = oA(t) X ffB(t) (190) diffusional motion701*713 and hydrodynamic effects,
r
which were accounted for by an rdependent diffusional
with U A and UB the single radical spin density matrices. tensor (Oseen's tensor).714
Numerical Integration by FiniteDifference Anisotropic reactivity has been taken into account by
Methods. The continuousdiffusion SLE and its nu admitting one angular degree of freedom in the spatial
merical integration by finitedifference methods have dependence of p. A discretization in the angular sub
been introduced and mainly exploited by Pedersen and space was achieved in terms of orthogonal expansion
Freed (cf. Table 20) in the theoretical study of CIDNP in a series of Legendre polynomials.725The problem of
and CIDEP effects. The advantage of this type of anisotropic reactivity has also been treated by Salik
technique is that any special r dependence of the hov,6= however, in a much simpler scheme of two dis
Hamiltonian (exchange interaction), the reactivity su crete rotational sites.
peroperator K ( r ) ,and the diffusional operator r ( r )may The first explicit results on the MFD of chemical
be taken into account in a straightforward manner, so reaction yields from numerical integration of the full
that no physically unreasonable assumptions have to SLE have been obtained by Werner et al.643 In their
128 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
calculations an explicit time integration by a finite cally impossible. The borderline case, however, where
difference method was also employed, yielding the time rdependent interactions are confined to an infinitesi
dependence of singlet and triplet recombination yields mal range of r in the form of &functions is amenable
under various conditions. Diffusion in a Coulombic to analytical solution. The density matrix elements may
potential and exchangemodified spin motion were be decoupled in the potentialfree regions using a
taken into account. For the zerofield case a model spinstate basis that diagonalizes the Hamiltonian. The
radical pair with one nuclear spin I = ‘/zon each radical btype potentials will cause discontinuities in the gra
was employed, whereas in the highfield limit a sum dient of p and may be accounted for by means of
mation over 625 independent solutions of 2 X 2 spin suitable boundary conditions at the boundary between
space problems for the realistic pyrene/DMA+ hy the two continuous regions of p and dp/ar.
perfine coupling situations was carried out. It was Evans et al.700were the first to use this method in a
found that the precise form of the exchange interaction quantitative theory of the CIDNP effect. Then the
significantly influences the recombination yields only method was adopted by Salikhov et a1.715p717 and by
in solvents of low polarity, where the Coulombic in H a b e r k ~ r n Further
. ~ ~ ~ ~contributions
~~~ are due to Ad
teraction can force the radical pair to remain in the rian and M o n ~ h i c kto, ~ S ~h ~~ ~s ~h ~i ~nand
, ~to~Mints
~ ~ ~ ~ ~
strongexchangeregion for a longer time. The influence and P ~ k h o v . ~ ~ ~
of exchange interaction on the relative magnetic field For an illustration of the method we shall outline the
effect on recombination yields is fairly weak. The nu procedure used by Haberkorn.682He used the following
merical solution of the full SLE problem corroborated form of rdependent operators in eq 120:
the results of much simpler integration procedures with &(r) = 4r)Qs (192)
an assembling of spin motion and diffusion by coupled
diffusion equations (cf. section 5), thus justifying the
application of the latter methods to study in detail the
solvent, temperature, magnetic field, and magnetic
isotope dependence of recombination yields.
De Kanter et al.346treated spinselective recombina
tion of biradicals by the continuousdiffusionSLE using K(r) = Itorob(r ro) (195)
a restricted diffusional model to describe the time de
pendence of the biradical endtoend distance distri and the initial condition was
bution. In this way the problem turned out to be more p(r, t = 0 ) = Porob(r  ro) (196)
tractable than using a multirotational isomeric state
model. The Ar increments were determined so as to Applying Laplace transformation in time and Fourier
receive equal endtoend distribution probabilities un transformation in space, eq 120 was transformed into
der equilibrium chainfolding conditions. The transi a matrix equation that could be formally solved and
tion rates Wklbetween adjacent Ar elements centered after Fourier transforming backward yielded the fol
at rk and rl were described by analogy with classical lowing matrix equation for p(ro):
Brownian motion with an effective diffusion constant pkdro) =
D ’:
Z ~ T D ( P, O~+ )iJo[Q~,P(ro)1  h0/2 [ QT,P (ro)1+ ) kl
Wk, = (D’/(n  o J 2 ) 6 k , ~ * , (191) (197)
Although Wklis r dependent, eq 191 is in accord with with
the correct equilibrium distribution, because Wk, = Wlb.
Since the Redfield relaxation matrix was included in zkl = 11  eXP(qkl)lrD/qkl (198)
the Liouville operator of spin motion, the whole prob
lem could not be partitioned into independent spin q k l = 2diwk1rD (199)
subspace problems. Thus only the simplest model +
radical pair with one nuclear spin ( I = was analyzed. Wkl = (Ck  q)/h (200)
The coupling of 20 matrix elements of the spin density
matrix had to be considered for determining the CID In eq 197 the eigenstates of the rindependent spin
NP effects, which, with 15 spatial increments of poly Hamiltonian with eigenvalues ti are used as basis states.
methylene chain endtoend distribution (C7biradical), The analogous result to eq 197, however for singlet
yielded a 302dimensional system of linear equations pair recombination only, had been derived by Evans et
which was numerically solved for variable values of Bo. aL7O0 Only in the highfield case a closedform analytical
Although the evaluation was not aimed at determining solution can be obtained. Since it is, however, a rather
the MFD of overall reaction yields, the conclusion that unwieldy expression, we shall quote here, in a form
the CIDNP results cannot be understood on the basis compatible with the symbols generally used in this
of a simple onesite radical pair model with an average section, the exact highfield results derived by Salik
exchange interaction is also valid for MFEs on overall hov715for the simpler case with neglect of exchange
quantum yields with covalently linked radical pairs as interaction and adapted to the case with a radiation
has been shown in detail by Schulten and cowork boundary condition a t r = ro = a.
ers.347,665,695
‘YS = C h m ( 2+ VI)) (201a)
Analytical Solutions. Although diffusion equations m
may be solved analytically for a great variety of
boundary conditions,731the rdependent mixing of spin = Ch,s(m) (201b)
m
density matrix elements by spindependent potentials
renders a general analytical solution of eq 120 practi with
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 129
A, = A/([2(1 + A ) + 6(m)(2 + A ) ] n ( I k+ 1)) (202a) ousdiffusion SLE have been worked out by Werner et
k al.643who applied numerical integration by finitedif
ference methods and by H a b e r k ~ r n ~in~ al manner
A = 4.1rr2krD (202b) similar to his timeintegrated solution method outlined
above. His result is presented as a series expansion in
6(m) = (u(m)rD)1/2 (202c) the matrix elements qkl defined above and is valid in
The u(m)are the highfield S/Totransition frequencies the socalled lowfrequency limit and at times longer
of radical pairs with nuclear spin states (m). than TD.
Mints and P ~ k h o have
v ~ ~also
~ solved the continuous The relatively modest interest in timedependent
diffusion SLE under highfield conditions but including theoretical treatments may be due to the fact that, until
also relaxational coupling to T+ and T. Neglecting recently, only few timeresolved measurements in the
exchange interaction and assuming singlet recombina nanosecond region have been available for MFEs on
tion at r = ro (radiation boundary condition), they de reaction yields. An exception to this is the situation in
rived analytical expressions for the recombination yields radioluminescence. Here, however, there is in general
sYs, TYs,and FYs. no spindependent recombination rate, and hence
Series expansions have been applied to solve eq 197 timedependent MFEs can be calculated with the as
for general fields. Whereas Evans et al.700considered sembling formalism of independent spin motion and
exchange interaction and recombination as small per diffusion, described in section 5.
turbations and applied an iterative procedure to im There is now an increasing amount of work dealing
prove solutions of p(ro),HaberkonP2 expanded p(ro) with timeresolved magnetic field effects in photosyn
in powers of qkl,which yields more general solutions, thetic reaction centers and in micellar solutions. For
since no restriction is imposed on the size of Jo and k,,. a proper understanding of these experiments more work
The solution is given to second order in qkl. on timedependent theories, which in the latter case
S h ~ s k i applied
n ~ ~ ~ perturbation methods to obtain should also include paramagnetic relaxation effects,
analytical expressions as solutions to the continuous would be desirable.
diffusion SLE, which included rdependent exchange
or Coulombic interaction in high magnetic fields, i.e., D. TripletTriplet and TripletDoublet Pairs
considering S/To transitions only. His results for the
case of exchange interaction compare favorably with the The main difference of theoretical treatments dealing
numerical results of Pedersen and Freed.713 Analytical with TT and TD pairs as compared to DD pairs results
approximations to the case of radical ion pair diffusion from the dominant role the zerofield splitting (ZFS)
in a Coulombic potential have been obtained under plays in triplets. Thus, in general, the influence of
limiting conditions of weak ( x << 1)and strong ( x >> 1) nuclear spin states is even neglected in such problems,
magnetic interaction,726where the parameter x is de so that the dimension of the pair spin space is at most
fined by 9, limiting the computational effort when aiming for
exact solutions.
x = 1/r,(~/2D)l/~ (203) A general treatment of TT and TD pair behavior in
with the Onsager radius rc given by a magnetic field will start with a SLE including similar
terms as eq 120 used for radical pairs.
eo2 With the exception of singlet fission, TT and TD
rc = 
4.lrtdT pairs are generated by random encounters, corre
sponding to the Fpair situation with radicals. In this
In a more general treatment of spindependent rad case a source term is included in the SLE accounting
ical ion pair recombination, S h u ~ h i demonstrated
n~~~ for the production of TT and TD pairs.
that the effect of Coulombic attraction corresponds to In the case of triplet fusion and triplet quenching by
exponential escape from a cage in the strongmagnet triplets, the source term is usually assumed in the
icinteraction case, whereas the free diffusion model is form73
a good approximation in the weakmagneticinteraction
case. G m = f/gknT216(r ro) (205)
7. TimeDependent Solutions of SLEs G m = 1/6kn~nd6(r ro) (206)
Few authors have determined timedependent solu Here nT and nDare the bulk concentrations of triplets
tions of radical pair recombination yields on the basis and doublets.
of direct solutions of SLEs. In the case of singlet fission the corresponding source
Within the framework of the exponential SLE, Tang term would bel3
and Norris707have calculated the time evolution of the GSF = ksQsG(r  ro) (207)
transient radical pair state in photosynthetic reaction
centers. They solved numerically the matrix equation The reaction operator K will have to account for
for the Laplace transform of the spin density matrix spinselective reaction into the singlet, triplet, or quintet
i ( s ) , from which p ( t ) was obtained by numerically channel (for TT pairs) or the doublet or quartet channel
performing the inverse Laplace transformation. (for TD pairs). For the TT case it may be written as736
Lendi705in his perturbational treatment of a general
exponentialtype SLE provided also timedependent KP = '/[(XsQs k XTQT k AQQQ),PI+ (208)
solutions valid in the limit of short and long times. The experimental quantities of interest are related to
Timedependent solutions on the basis of the continu stationary flow rates rs and rD into the singlet channel
130 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
C, crystal; S, solution; I, interface or surface. bZerofieldand highfield situation, anticipation of highfield resonances. E, exponential
type; D, diffusional type SLE. Derivation of highfield resonance line shape. e Spin relaxation included. 'Twodimensional diffusion.
#Derived as limiting case. hTransitions between pair spin states assumed to be due to hfc. 'Discussion of potential CIDNP in triplet
carbene dimerization. Independent suggestion. Description in terms of coherent spin motion. Averaging over static angular distribution
J
of pairs. Case of triplet quenching by oxygen. "Estimation of highfield effect. First dynamical treatment, taking molecular motion in
solution into account. PComplete field dependence for various pair parameters. *Analytical expression for field dependence in the direction
of lowfield resonances. Taking into account anisotropy of spin relaxation. Effect due to Boltzmann distribution under highfield, low
temperature conditions. Dvnamical and statistical case of molecular motion. Onlv spin motion, no recombination vields evaluated.
(in the case of delayed fluorescence) or the doublet and the stochastic operator r(r,B)of eq 120 is reduced
channel (in the case of triplet quenching by doublets to a monoexponential dissociation rate constant kl.
or chargecarrier detrapping). The stationary rates rs The rotational degree of freedom B is also omitted, since
or r D may be used to define effective reaction proba in the crystal all the triplet excitons have the same
bilities y for triplettriplet or tripletdoublet encoun orientation and cannot rotate. The spin Hamiltonian
ters: H is usually taken as a simple superposition of the in
dividual triplet spin Hamiltonians, neglecting any ex
rs = ')"knT2 (209) change interaction.
= H T ( l ) + HT(2) (213)
which was originally suggested by Merrifield on intui one energy eigenstate only. From the line width A of
tive arguments.7I It corresponds to a superposition of the highfield resonances the ratio k2/ kAl can be de
independently decaying energy eigenstates with a spe termined. In order to fix the absolute values of these
cific annihilation rate constant of k21Si12,proportional rate constants, fitting to the complete MFD is required.
to their singlet character (cf. section 11). The result thus obtained for anthracene73was kl = 2.8
The coefficients Si depend on the magnetic field X lo9 sl and k2 = 1.1 X lo9 s'.
strength and direction. Whereas a t zero field lSiI2 is The formalism described so far for TT pairs may be
distributed over three eigenstates (if we deal with triplet applied in an analogous way to TD pairs, too. Corre
pairs with parallel orientation of the ZFS tensor axes), sponding formulas have been derived by Bouchriha et
it will be mixed into more energy eigenstates as the al.235Since the exponential SLE approach of Johnson
magnetic field increases, as long as gpBBo does not and Merrifield73corresponds to a kinetic description of
greatly exceed the zerofield splitting. Due to the ori the TT annihilation process in terms of rate constants
entational dependence of the ISiI2 coefficients in this (scheme 211), which may be an oversimplified model
field region, the socalled lowfield resonances may be of physical reality, Suna456studied the kinematics of
observed as the crystals are rotated in a constant triplet exciton annihilation in molecular crystals on the
magnetic field. Such resonance orientations are en basis of the full rdependent SLE analogue of eq 120.
countered where Bo is parallel to either of x * , y*, or z*, The stochastic motion (r(r))of the TT pair was rep
the main axes of the triplet exciton ZFS tensor. Com resented either by a continuous differential operator or
pact analytical expressions for the field dependence of by a difference operator, modeling the hoppingtype
yTT with Bo along such lowfield resonance directions diffusion of excitons in a crystal. Restricting the re
have been derived by Le~in.~O activity operator K ( r ) to nearestneighbor interactions,
Kubarev et a1.735investigated the situation of tet Suna obtained analytical solutions for the spininde
racene/oxygen triplet pairs with a specific orientation pendent case with one, two, and three dimensions of
of the oxygen molecules. Using the Merrifield for diffusion. He showed clearly that only in the three
malism, they calculated the MFE on the rate constant dimensional case is there a unique definition of a sta
of singlet oxygen production. They obtained several tionary diffusioncontrolled recombination rate con
orientational resonances for magnetic fields where the stant. In this case a certain isomorphism between
Zeeman energy is in the order of magnitude of 302 ZFS. diffusional and kinetic (exponential) models exists,
When gpBBo largely exceeds the ZFS, the (TT)pair whereby the following relation holds true:
singlet character is concentrated on fewer energy ei
genstates than in zero field, so that the triplettriplet k2/k1 = AU/kdiff (220)
annihilation rate constant drops below the zerofield
value. At very high fields the singlet pair state is disHere kdiff is the diffusioncontrolled bimolecular re
tributed over two energy eigenstates only, with JSiI2 combination rate constant and X is a firstorder reaction
=
1 / 3 and IS212= 2 / 3 . Then the limiting value of yTTisrate constant, which is assumed to be uniform within
the reaction volume u. In one or two dimensions such
a relation does not generally exist because there will be
complete recombination even for very small A, since in
these reduced dimensions there is an infinite number
(217) of reencounters of the pair. Only if a unimolecular
decay of the triplet excitons determines their bulk
In general, with solution of the spinHamiltonian concentration can effective values of a diffusioncon
eigenvalue problem, eq 216 has served to obtain rea trolled reaction rate constant and the ratio k,/ kl be
sonable quantitative fits of the magnetic field strength unambiguously defined.
and orientational dependence of delayed fluore~cence.~~ The spindependent problem was solved by using the
The two highfield levels, which carry all the singlet continuousdiffusion form of r(r) and restricting H(r)
character, become degenerate at certain directions of and K(r) to nearestneighbor interactions. The Green's
the magnetic field (cf. Figure 11). A level crossing oc function technique was applied to transform the con
curs, which causes the socalled highfield resonances. tinuousdiffusion SLE to a linear matrix equation.
The line shape of these may be obtained from the SLE With this procedure Suna anticipated the techniques
for a reduced 2 X 2 density matrix, with the result73 later used by Evans et aL700 and Haberkorn682for the
treatment of the radical pair mechanism with Bfunc
tional type exchange and reactivity terms. Further
more, Suna incorporated the effect of spin relaxation
using, however, one relaxation parameter only.
This form of the theory was applied to analyze the
experimental results on TT annihilation in anthracene
crystals. This system actually represents a case of a
(219b) twodimensional exciton diffusion in the crystallo
graphic ab plane with relatively slow hopping in the c
direction between the planes. The hopping rate be
(k1 + M(k1 + k2/2)' tween the planes could be treated as a monomolecular
A2 = (219~)
kl(k1 + k2/3)(k1 + 2k2/3) exciton decay whereas the diffusion in the plane pro
vided a model for the reencounter kinematics of the TT
At exact resonance yrrHF(0) = y'(m); Le., the situation pairs. The relation to the Johnson and Merrifield pa
corresponds to a concentration of singlet character on rameters k2 and kl was established and related to
132 Chemical Reviews, 1989, Vol. 89, No. 1 Steiner and Ulrich
E. ReactfonYieldDetected Magnetic
Resonance
Although there are cases where microwaveinduced
effects on chemical reaction yields can be observed at Figure 50. Synopsis of MARY spectrum, RYDMR spectrum,
zero field (cf., e.g., the method of zerofield ODMR in and the El spectrum as detectable from the relative triplet yield
molecular triplet spectroscopy), in most cases the of recombining radical pairs generated with singlet spin alignment.
RYDMR effects observed represent microwaveinduced Reprinted from ref 93 with kind permission of M. E. Michel
Beyerle; copyright 1983 Elsevier Science Publishers B.V.
modifications of effects from static magnetic fields on
reaction yields. Generally speaking, the reaction yield
may be expressed as a function Y(Bo,Bl,o)and the to use this approach in order to estimate the B1 strength
various kinds of “magnetic spectra” (MARY, RYDMR, necessary to detect RYDMR effects for radical pair
BJ may be envisaged as appropriate projections of this recombination in solution.
function as has been demonstrated in a synoptic dia Treatments of the RYDMR line shape based on a
gram by Lersch and MichelBeyerleg3 (cf. Figure 50). more general spin motion have been reported by Ku
The development of RYDMR theories has been barev et a1.7371738
and by Doktorov et al.741 Here, e.g.,
closely related to experimental work going on in the for a singletproduced radical pair in a definite nuclear
field. Thus, mechanistically, the emphasis has been on spin state, the spin motion under highfield static
reactions involving DD and TT pairs. Furthermore, for magnetic field conditions and at arbitrary S/To cou
DD pairs all the treatments applied so far refer to the pling strength A(STo)is given by737J38
socalled “highfield” case; i.e., only S/To mixing is ‘ps = A + B COS [ ( Q l + Q2)t] + C COS [ ( Q ,  QJt] +
considered as a microwaveindependent ISC mecha D[COS(nit)+ COS (Q,t)](229)
nism, and nuclear spin states are considered as sta
tionary so that the total problem can be solved as a with
superposition of independent solutions for an ensemble
of radical pairs with different nuclear spin states. A
Q1,2 = [(aof A(STo)/2  w ) ~ w12]1/2 (229a) +
survey of original references, dealing theoretically with where wo is the average Larmor frequency of both rad
RYDMR effects, is given in Table 22. icals in their respective nuclear spin states, w is the
microwave frequency, and w1 the Rabi frequency, de
1. Kinetic Schemes with QuasiStationary Spin States fined as
The easiest situation to deal with theoretically is w1 = gpBB1/ h (230)
when the eigenstates of the timeindependent part of where gfactor differences can be usually neglected.
the spin Hamiltonian are clearly separated with respect The coefficients A to D are given by
to their kinetic width. Then the effect of resonant
microwaves may be described as inducing transitions A=B+C (231a)
between the quasistationary spin levels, and the overall
kinetics may be treated by a set of coupled kinetic rate B = f/2 sin4 [(e,  6,)/2] (231b)
equations for the populations. This method, which
corresponds to the simple Merrifield model in the case c = ‘/2 cos4 [(e,  e2)/2] (231c)
of nonresonant magnetic field effects, has been applied D = y4 sin2 [e,  e,] (231d)
by Ruedin et al.736for ODMR with Fcenter pairs (DD
case) in alkali halide crystals and by Frankevich et with
a1.10615441547
for RYDMR observed by delayed and sin e1,2 = Wl/Ql,2 (232a)
prompt fluorescence in organic molecular crystals (TT
and TD case; for a review of this and other RYDMR COS 01,2 +
= (wo A(STo)/2  w)/Ql,2 (232b)
work, cf. Frankevich and Kubarev41). The radical pair recombination yield was calculated
Within these approaches the linewidth problem is by integrating over an exponential decay function741or
handled by using the usual ESR linewidth expression using a reencounter probability function based on the
for the frequency dependence of the microwaveinduced continuousdiffusion equation.738 If wl, 7l << A(STo)
transition rate. (7 is the lifetime of the radical pair), each nuclear spin
configuration gives rise to a doublet of RYDMR lines
2. Spin Motion in a Microwave Magnetic Field separated by A(STo). Under such conditions and for
an exponential decay of the radical pair with time
In liquid solutions it was logical to extend the concept constant T~ the line width Aw of each doublet compo
of spinmotionmodified recombination kinetics (cf.
section V.C.5) to include also the influence of a micro nents is given by
wave field. Kubarev and Pschenichn09~were the first Aw = ( 1 / ~ k
2 w12)1/2 (233)
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 135
conductivity. Also analysis of delaynarrowing effect in timeselected observation. Critical comparison of RYDMR and MARY method.
"Also RYDMR anisotropy. O Also time integration with f 0: t3/2. PIncluding exchange narrowing by electron hopping. PDiffusion in
Coulombic potential. Dependence of RYDMR intensity on diffusion parameters. hfc treated as perturbation. Analytical conditions for
line maxima and minima. "Case of &Bo >> gB1,coherent MW transitions, recombination yield averaged over one period.
solved approximately by timedependent expansion of microwave field B1. Special emphasis was put on the
the spin density matrix. An analytical solution was analysis of Bldependence and anisotropy of the
obtained for the limiting case of low singletpair re RYDMR spectra.
activity with respect to the dissociation rate of the TT Tang and N ~ r r i presented
s ~ ~ ~ a similar analysis of
pair. The RYDMR line vanishes at the levelcrossing reaction center RYDMR spectra, derived from a nu
position because here the kinetically active spin states merical solution of the exponential SLE under sta
are effectively pure singlet and quintet. In terms of tionary conditions. They used a Gaussian distribution
Figure 51 the variation investigated would correspond of hyperfine couplings modeling the realistic situation
to a decrease of the energy gap A(STo),which in the in reaction centers. The results were averaged over a
present case corresponds to A(SQ,J, whereas T+and T discrete orientational distribution of reaction centers.
should be substituted by Q1 and Ql. Special attention was paid to the relative influence of
The notion of spin conservation in geminate elec Bl and singlettriplet splitting parameters J on the line
tron/hole pairs as a principal idea to explain resonant shape. A maximum in the B1 spectrum occurs if B1=
microwave effects on photoconductivity in semicon 2J, the ST energy gap.
ductors was introduced by Kaplan, Solomon, and Hunter et a1.744and Lersch and M i ~ h e l  B e y e r l e ~ ~ ~
M ~ t t The ~ ~ of this mechanism to the situation
. ~ relation provided analytical expressions for the RYDMR line
in radical pair theory has been recognized by Haberkorn shape of reaction centers under the limiting condition
and D i e t ~ , who
5 ~ ~applied the exponential SLE method of small hyperfine couplings, so that they may be
involving a &type S/To coupling. treated as perturbations in the effective Hamiltonian.
In the rotating frame their SLE assumes the form According to Lersch and MichelBeyerle, the relative
RYDMR intensity is given by
p(t) = i(H'p  pH8) (234)
with the effective (nonHermitian) Hamiltonian

and Q is given by eq 229a with A(STo) 0. Note,
(240a)
the DD pair. The parameters ks and kD denote the rate
constants of singletpair recombination and pair dis
sociation, respectively.
In the case (wo  w d ) >> ks, kD, wl, wl' the solution of

however, that the result (240) is not valid in the limit
ks/kT 0. A corresponding correction is given in ref
745.
eq 234 corresponds to a wellresolved doublet of lines, Hunter et a1.744applied these solutions to fit exper
for which an exact analytical lineshape formula has imental temperaturedependent RYDMR spectra. The
been given. The recombination yield FYsas a function observed RYDMR spectra were well reproduced by the
of o,e.g., in the range of the unprimed resonances, is assumption of temperaturedependent values of J and
the recombination rate constants ks and kT. Lersch and
 1 /2ks(ks + 2kD)'(1 + KW1'[(WO  w)' + (kD +
F yS 
MichelBeyerle7&derived analytical conditions between
k,/4)'(1 + u i 2 / k ~ ( b+ ks/2))1'I (237) the parameter values corresponding to characteristic
limiting cases of the RYDMR line shape.
with The RYDMR lineshape effects as determined by the
K = 1 / ( k S / k D ) ( k ~ k k s / 4 ) ( k ~ ks/2)' (238) ratio of microwave power and exchange interaction,
discussed in ref 93 and 742745, may be qualitatively
Actually, this case treated by Haberkorn and Dietz with understood from the level crossing/anticrossing diagram
its limiting conditions for the analytical solution is depicted in Figure 52, illustrating the rationales given
kinetically equivalent to the situation treated with the by Lersch and M i ~ h e l  B e y e r l eand
~ ~ ~by Tang and
integrated spin motion method by Kubarev and N o r r i ~ The
. ~ ~relative
~ energies of the spin states are
P s c h e n i ~ h n o v .However,
~~~ the relation between the represented in the rotating frame as functions of o,
results of these treatments is not obvious and has not whereby singlet and triplet mixing terms are considered
been analyzed. as small perturbations, not to be seen in the diagram
The need for an interpretation of RYDMR spectra (actually the S/t crossings would be weakly avoided).
observed with photosynthetic reaction centers has The S/T splitting is indicated as 2J. The directions
stimulated some theoretic@ work which has been based of spin quantization in the triplet eigenstates of HM
on the exponential SLE in the rotating frame (cf. eq depend on w and on the Rabi frequency wl. Thus,
234). whereas far from resonance t+,to, and t correspond to
Lersch and M i ~ h e l  B e y e r l ederived
~~,~~~ a timede T+,To,and T.., quantized along Bo,at resonance t+,to,
pendent result for the recombination yield of triplets and t are completely quantized along Bl so that here
starting from the formal solution to eq 234: Tois equally distributed over t+ and t and tois a 1:l
p ( t ) = exp(iH't)p(O) exp(iHRt) (239) mixture of T+ and T. Since in a high Bo field sin
glettriplet transitions occur via S/To coupling, the
which has been evaluated by numerically diagonalizing efficiency of this process as a function of w will depend
the effective spin Hamiltonian matrix. RYDMR on how To is distributed over the t states and on the
spectra were calculated for a twoproton model, taking energy gaps between S and t+,to,and t in relation to
into account the effect of exchange interaction J, an 01.745 The size of w1 is expressed in the width of the
isotropic dipolar spinspin interaction D, and variable t+/t anticrossing at the resonance position.
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989, Vol. 89, No. 1 137
correspond to nuclear triplets and are combined with where wop is the frequency corresponding to the o / p
odd rotational states748): rotational energy difference and r is a composite cor
relation time given by
1/r = 1 / T C + 1 / r p (245)
with TC, the diffusional correlation time of the hydrogen
molecules with respect to the paramagnetic centers on
In eq 243 I d = 1 and I+ = 1 / 2 are the spins and p d and the surface and ~ p the , paramagnetic relaxation time
pp the magnetic moments of deuteron and proton, re of the spin component vertical to the surface. The
spectively. In the derivation of eq 243 details of the shorter time of both determines the motional degree of
collision dynamics have been omitted since these were freedom providing most of the energy to be exchanged
considered to contribute equal factors to the rates, if in the o/pH2 conversion process.
these are compared a t temperatures T and T/2, where The timecorrelation functional approach has been
thermal distributions of momenta in H2 and D2 are applied also by Petzinger and S ~ a l a p i n owho, ~ ~made
equal. use of a tensor operator formalism to handle dipolar
Farkas and G a r b a t ~ k iused
~ ~ ~both a generalized interactions and correlation functions. They obtained
Wigner formalism for thermally averaged conversion absolute rates in terms of physical parameters that are
rates of o/pH2 and o/pD2 and the Kalckar and Teller helpful to analyze experimental results. Thus the
expression, eq 243, to evaluate the ratio of the magnetic motion of the H2 molecule on the surface was treated
moments of proton and deuteron from their experi as a twodimensional MaxwellBoltzmann gas or by
mental rates. The result from the Wigner treatment twodimensional diffusion. Otherwise the rate of de
corresponded more closely to the accepted ratio of the sorption was assumed to determine the translational
magnetic moments than that obtained from the Kalckar correlation function of H2. A similar theoretical ap
and Teller expression. proach was used by Atkins and C l ~ g s t o to n ~deal
~ with
The most advanced treatment of paramagnetically catalytic o/pH2 conversion in solution. The results
catalyzed o/pH2 conversion in the gas phase has been have been applied to determine the firsthydration shell
given by Nielson and Dahler,750who applied a full radii of transitionmetal ions from their catalytic ac
scattering theory formalism. Numerical results were tivities in o/pH2 conversion.
obtained for O2as catalyst using a hardcore intermo Special efforts toward an understanding of the ex
lecular potential. The absolute rates obtained theo ternal magnetic field modulation of the catalytic o/pH2
retically are by a factor of 34 smaller than the exper by solid magnetic surfaces have been made by Ilisca and
imental ones. Possibly these results may be further c ~  w o r k e r s . ~ ~ In
' ~ ferromagnetics
J ~ ~  ~ ~ ~ such a change
improved by applying the new XYcoupling mecha in the catalytic activity in a magnetic field may be due
nism81 instead of the Wigner mechanism. to a change of the magnetic polarization director with
The catalytic o/pH2 conversion on paramagnetic respect to the magnetic surfaces whereby a significant
surfaces was initially treated in a way similar to Wig change in the amplitude of the time correlation function
ner's gasphase theory, however taking into account that of the paramagnetic spin component vertical to the
the adsorbed hydrogen molecules undergo more con surface may ensue which is responsible for the o/pH2
tacts with paramagnetic centers than in the gas conversion process.757
phase.751p752Including the adsorption equilibrium may More recently, Ilisca et a1.83p758gave a very detailed
cause an overall negative energy of activation for re tensorial analysis of the theoretical rate of o/pH2
action rates catalyzed by paramagnetic s u r f a c e ~ ~ ~conversion
~ on paramagnetic surfaces. This approach
whereas the Wigner mechanism in the gas phase should was based on the Wangness and Bloch e x p r e s ~ i o nfor ~~
yield rates monotonically increasing with temperature. the rate of irreversible processes. The quantum degrees
In a theoretical treatment by Leffler753the o/pH2 of freedom that are explicitly taken into account are the
conversion mechanism on magnetic surfaces is ascribed H2 rotational angular momentum (L),nuclear spin (I),
to different nuclear relaxation rates of the two H, and the electronic spin of the paramagnetic center (S).
protons, caused by their different distance from the Allowance for a polarization of the partial density ma
paramagnetic surface centers (it has been assumed that trix in the space of these dynamic variables is made,
the H2 molecules are oriented perpendicular to the whereas the density matrix of the H2 translational
surface). The paramagnetic spins are thought to induce motion is assumed to correspond to the thermal equi
proton nuclear relaxation by dipolar spin coupling librium throughout. The conversion rate may be cast
which is rapidly modulated with a correlation time in the form
characteristic of the Paramagnetic spin relaxation. The K p = Tr {EPJ (246)
absolute values estimated by this method are larger
than the experimental ones. The conclusion that a where p is the stationary state density matrix in the
paramagnetic catalyst should be more efficient the basis of L, I , and S eigenstates and E is a reaction
longer the paramagnetic spin relaxation rate has been efficiency operator. An expansion of this expression
criticized by Ilisca et a1.,754,755
who derived a rate ex into a sum of irreducible tensor operators products is
pression for catalytical o/pH2 conversion on a magnetic performed, which forms a natural basis for a physically
surface by timeintegrating the correlation function of meaningful decomposition of the rate into contributions
perturbation matrix elements providing the coupling of various multipole polarizations and reactivities. A
between appropriate rotational levels of 0H2 and pH,. major conclusion from the analysis is that with p cor
The transition rate was responding to thermal equilibrium the order of mag
nitude of the experimentally observed magnetic field
W0lpa 2r/(1 + wop2r2) (244) effects cannot be explained. Thus one has to conclude
Magnetic Field Effects in Chemical Kinetics Chemical Reviews, 1989,Vol. 89,No. 1 139
that in the steady state of the reaction there is a con “supramolecular” arrangements as the chemically linked
siderable degree of alignment of paramagnetic spins and electron donoracceptor systems. Radical pairs in
nuclear spins ( S I polarization) or of rotational angular suitable microreactors can be also conceived as exam
momentum and nuclear spins (LI polarization). It is ples of such supramolecular chemistry.
also pointed out that, whereas the antisymmetric part Whereas theories of the radical pair mechanism in
of the interaction Hamiltonian (cf. eq 241) is important homogeneous solutions appear to be well developed,
for effecting ortho/para transitions, the symmetric part there is so far no quantitative understanding of the
is likewise of importance in that it is responsible for the magnetic field dependence of geminate radical pair
dynamic polarization effects mentioned. This impor kinetics in micellar and microemulsion type supercages.
tant feature had not been noticed before. Pertinent theoretical developments are needed, which
A specific model explaining how such polarizations would in particular have to focus on the magnetic field
may arise has been described by Ilisca and D e b a ~ c h e . ~ ~dependence
~ (up to high fields) of various mechanisms
They suggested that the impinging H2 molecules librate of electron spin relaxation. A novel access to the details
on the catalyst surface, thus creating a fluctuating of rotational and translational diffusion of radical pairs
magnetic field that polarizes the neighboring magnetic should result from an application of these theories to
impurities. These polarizations are maintained by the magnetokinetic effects in such media.
continuous exchange of the H2 molecules. Application As for the magnetic isotope effect ensuing from the
of an external magnetic field leads to an enhancement radical pair mechanism, there remains a wide field of
of the polarization and hence also of the catalytic rate. isotopes to be explored throughout the periodic table.
Finding convenient chemical systems and reactions to
V I . Conclusion exploit such effects for magnetic isotope separation
should represent a great challenge to chemists and
photochemists.
In this review we have tried to give an adequate and There is recent evidence that the magnetic coupling
clearly structured, comprehensive representation of the of spin and orbital momentum in orbitally degenerate
present scope of the field of magnetokinetics, whereby states of transitionmetal c ~ m p l e x e ~ ~ ~ ~ ~ ~ ~
we have attempted to put equal weights on both the may cause appreciable magnetokinetic effects at fields
theoretical and the experimental point of view. At in the range of several tesla. The intriguing theoretical
tention was focused on the basic mechanistic principles problem about this type of phenomena is the way
and their mutual relations, on the diversity of experi spectroscopic information, mainly available from low
mental methods applied to trace magnetokinetic effects, temperature paramagnetic resonance and magnetoop
on the great variety of chemical systems, where they tical investigations in the solid state, can be utilized in
appear, and finally on the theoretical techniques de an appropriate dynamical description including the role
veloped for their qualitative and quantitative under of molecular motion during chemical reactions in liquid
standing. We hope that the frontiers of these devel solutions.
opments have been made clear and that the review will These examples may suffice to substantiate our con
stimulate further research leading toward an increasing viction that magnetokinetics will continue to establish
coherence of the field and a growing utilization of its itself as a distinguished field of chemical research, being
innovation potential. Looking into the near future, we attractive in its own right and a useful tool for inves
believe there is reason to anticipate substantial progress, tigating and furthering our understanding of the details
e.g., along the following lines. of chemical dynamics.
Experimental methods will certainly continue to be
improved with respect to sensitivity and reproducibility Acknowledgments. We are indebted to Dr. K. A.
in various domains of time resolution. If it became McLauchlan for critically reading the manuscript and
possible to achieve routine access to magnetic field for helpful comments. Financial support by the
effects below 1% , this would greatly extend the general Deutsche Forschungsgemeinschaft and by the Fonds
applicability of magnetokinetics as a tool for investi der Chemischen Industrie is gratefully acknowledged.
gating reaction mechanisms.
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