Chemical Physics Letters 535 (2012) 63–68

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Chemical Physics Letters

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Evidence of dual channel electron transfer induced negative magnetic field

effect on exciplex emission at very high permittivity of medium
Amit Kumar Jana, Partha Roy, Deb Narayan Nath ⇑
Department of Physical Chemistry, Indian Association for the Cultivation of Science, 2A & 2B Raja S.C. Mullick Road, Jadavpur, Kolkata 700032, India

a r t i c l e i n f o a b s t r a c t

Article history: Magnetic field induced change in the pyrene-N,N-dimethylaniline exciplex fluorescence has been studied
Received 3 February 2012 in condensed phase with very high permittivity. In contrast to the commonly observed enhancement of
In final form 16 March 2012 exciplex fluorescence in presence of magnetic field (for 7 < e < 33), the effect shows a complete reversal at
Available online 23 March 2012
low DMA concentration in DMSO which is observed only at the blue end of fluorescence. At high DMA
concentration the negative MFE at blue end slowly reverts back to the normal. At the red end of the emis-
sion the MFE retains its normal character for all donor concentrations even at very high permittivity.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction
The magnetic field effect (MFE) on reactions involving radical
pairs is an established and well understood phenomenon [1–12].
The effects observed since early seventies are today based on solid
theoretical background and experimental evidences. A direct en-
ergy consideration can not explain the effect and in condensed
phase the effect is mediated through a co-operative mixing mech-
anism which causes an intersystem crossing (ISC) between the sin-
glet and triplet states of the radical pair and thus modulates the
reaction pathways. Photo-induced electron transfer (PIET) between
an acceptor and donor producing radical ion pair is a special case.
In this respect pyrene is a common well studied fluorophore
and with N,N-dimethylaniline (DMA) it constitutes the popular
Py-DMA exciplex system in condensed phase. In this system singlet
excited pyrene acts as an acceptor and charge transfer (CT) from
the DMA molecule produces a pyrene anion and DMA cation in
the condensed phase at the encounter distance and this precursor
radical ion pair (RIP) is essentially in singlet state. In the geminate
recombination process the RIPs separate out to an inter-radical dis-
tance rST where the singlet and triplet states are degenerate and
some mixing mechanism like electron-nuclear hyperfine (HFI)
interaction of the lone electron with the radical nucleii or the dif-
ference in Lande-g factors of the two electrons (Dg effect in pres-
ence of external magnetic field) of the radicals causes a
multiplicity change of the RIPs. The singlet RIP eventually recom-
bines to contact ion pair (CIP) which is the luminescent exciplex
and the triplet mainly undergoes solvation to the bulk. Some of
the triplet RIPs also recombine to form 3Py⁄ and some singlet RIPs
also undergo solvation. In the absence of any external magnetic
field singlet and the three triplet states of the RIP are degenerate
⇑ Corresponding author. Fax: +91 33 2473 2805.
E-mail address: pcdnn@iacs.res.in (D.N. Nath).
and HFI causes transition from singlet to all three triplet states.
In presence of magnetic field (B), T+ and T states become non-
degenerate with S state and triplet leakage reduces causing an in-
crease in singlet exciplex luminescence. At saturating magnetic
field (a few hundreds of gauss) the triplet leakage essentially be-
comes one-third. The Dg effect, on the other hand, causes a mixing
between S and T0 only and the ISC rate increases with the applied
magnetic field. The singlet population thus suffers a decrease.
However, for organic radicals containing no heavy atom,
Dg  0.001 and for a substantial magnetic field effect B should be
of the order of 105 G. Thus in the domain of laboratory field of
the order of a few hundred gauss the HFI mechanism prevails in
Py-DMA system and MFE on exciplex luminescence is generally
positive.
In literature MFE on Py-DMA system has been studied in con-
densed phases of varying value of permittivity [13–23]. However
all these studies have been made in the permittivity range
7 < e < 33 and in all cases the MFE is positive for all values of
DMA concentrations as expected. Remarkably study of MFE at
higher permittivity remained unexplored due to high solvation of
the RIP states. The Coulomb energy surface essentially becomes flat
and consequently the exciplex emission band observed in a fluo-
rimeter also becomes a flat plateau above 460 nm without showing
the least curvature due to exciplex emission peak. We were inter-
ested to study the MFE in this domain (e  47) for the following
two reasons:
(1) The Onsagar radius at this value of permittivity becomes on
the order of 12 Å. The large dielectric screening of the med-
ium reduces the Coulomb attraction between the radicals
and the effective CT distance increases, the process more
and more falls in the domain of remote electron transfer.
The role of solvent molecules in the CT process becomes
more important. The excited Frank–Condon state of the

0009-2614/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
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64 A.K. Jana et al. / Chemical Physics Letters 535 (2012) 63–68
1.8x107
Intensity (cps)
1.2x107
6.0x106
0.0
350 400 450 500
Wavelength (nm)
(a)
Figure 1. Emission spectra of Pyrene-DMA exciplex system in DMSO where Pyrene was excited at 345 nm; (a) [Pyrene] : [DMA] = 104 (M) : 0.27  102 (M); (b) [Pyrene] :
[DMA] = 104 (M) : 19.8  102 (M).
acceptor and donor molecules may also get contribution
from the orbitals of the solvent molecule. The basic CT pro-
cess may show new properties. The super-exchange mecha-
nism operating in the system will effectively treat the
acceptor, donor and the solvent molecules as a super-
molecular assembly and this may lead to stabilization of
the RIP state.
(2) The second interesting feature of very high permittivity is
that the RIP energy may go down below the 3Py⁄ energy
level. In the permittivity range so far studied the RIP energy
is above the 3Py⁄ energy. This favors the recombination of
triplet RIP yielding 3Py⁄. It is through the delayed fluores-
cence produced by pyrene triplet–triplet recombination,
the MFE in radical pair system has also been observed [15]
and in this case the CT process essentially leads to a singlet
precursor RIP. However, at very high permittivity if the RIP
energy falls below 3Py⁄ energy, an interesting situation
may arise. Direct ISC mechanism in 1Py⁄ will lead to forma-
tion of 3Py⁄ which through CT will generate triplet precursor
RIPs. The observed MFE on the singlet luminescent exciplex
will turn out to be negative under such situation.
It is clear that the exciplex luminescence (u) at such very high
permittivity (DMSO, e  47; propylene carbonate, e  65) will be
very small and the resultant MFE, (Du/u) will be difficult to detect.
We have used the modulation technique and with state-of-art
Lock-in device and electronics it has been possible to detect the
MFE to an extent of 0.036% under working condition.
2. Materials and methods
Pyrene has been re-crystallized from ethanol–water mixture
before use. DMA (Aldrich) is used after vacuum distillation. All sol-
vents (Aldrich, HPLC grade) are used as supplied. All the samples
were deoxygenated by bubbling pure argon for 30 min. Each read-
ing is taken from fresh sample and each data is the average of six
readings. The fluorescence of the samples is measured by a
Fluoro-Max-3 (Jovin Yvon Horiba) spectrophotometer.
An improved version of phase-locked detection system has
been used to monitor the MFE. The light from a current stabilized
150 W xenon lamp after filtering through IR and visible cut-off fil-
ters and appropriate collimating optics, is passed through a small
hole in one pole of a home made ferrite electromagnet. The effec-
tive excitation band is from 330 to 375 nm. The luminescence from
550 600 350 400 450 500 550 600
Wavelength (nm)
(b)
the sample placed inside the electromagnet is collected trans-
versely by the conventional double lens optics and is passed
through a monochromator (f/3.4) with final detection by 1P28
PMT with a load impedance of 1 MX biased at 400 V. The maxi-
mum anode signal current drawn from the PMT is on the order of
30 nA which gives 30 mV output voltage. The linearity of the PMT
output in this range has been tested by neutral density filters (wire
mesh) which are calibrated by Shimadzu UV-240PC UV–VIS
absorption spectrophotometer in transmission mode. The sinusoid
waveform from an INSTEK GFG-3015 function generator
(14.1 Hz, f) is fed into 50 W power amplifier (Radio Shack) which
drives the electromagnet. The resulting 28.2 Hz (2f) modulated
ac component of the luminescence with amplitude E2f at saturating
magnetic field (BM = 200G) [E2f = (2/p)(2/3).Du] is amplified by a
home-made sharp tuned (28.2 Hz) low noise amplifier followed
by synchronous detection in SR830 Lock-in amplifier. The tuned
amplifier has gain on the order of 50 dB and a bandwidth of
0.9 Hz. The gain curve of the tuned amplifier is made flat over a
range from 28.14 to 28.28 Hz. The phase shift error due to thermal
shift of centre frequency is thus minimized. The Lock-in amplifier
(SR830) is operated in ‘HIGH RESERVE’ mode under an effective
noise bandwidth 0.0125 Hz with a response time of 80 s. The peak
input noise of the detection electronics is on the order of 45 nV.
However, it is the optical shot noise in the xenon light and the
noise introduced by the PMT in the amplification process which
limits the detection of MFE. For a 30 mV value of u the detection
limit of MFE is on the order of 0.03%. It is essential to have this sen-
sitivity to observe the negative MFE.
3. Results and discussion
Figure 1 depicts the emission spectra of Py-DMA exciplex sys-
tem in DMSO excited at 345 nm at two extreme DMA concentra-
tions used in our experiment. The spectra are essentially flat
above 460 nm. The background noise count for only DMSO is on
the order of 600 over the range. For [DMA] = 0.27  102 M the sig-
nal count at 600 nm is on the order of 66 765 and that for
[DMA] = 19.8  102 M is on the order of 57 709. For comparison
the signal count at the pyrene peak (k = 374 nm) for low DMA sys-
tem is on the order of 1.587  107. The spectra do indicate that
there is exciplex emission in both cases though it is flat over the
range. Figure 2 depicts the raw experimental graphs on the chart
recorder indicating the MFE on the exciplex system in typical
experiments. The sample is placed in an ac magnetic field
 A.K. Jana et al. / Chemical Physics Letters 535 (2012) 63–68 65

BM BM BM
200G
200G 200G
0 0
0

0 0 0
E0 E0 E0
-200mV = 24.0 mV -200mV
200mV = 17.6 mV = 15.2 mV
-200mV
200mV
0 8 min 0 10 min 0 10 min
(a) (b) (c)
BM BM BM
200G 200G 200G
0 0 0

0
+40mV +40mV
E0
0 0
-200mV = 19.2 mV E0 = 0.68 mV E0 = 0.60 mV
0 10 min 0 8 min 0 10 min
(d) (e) (f)
BM BM

200G 200G
0 0
+40mV
0 0
E0 E0
= 15.2 mV = 0.60 mV
-200mV
0 18 min 0 18 min
(g) (h)
Figure 2. Experimental graphs of lock-in output in response to a.c. magnetic field (B = BM Sinxt) in Pyrene-DMA exciplex system; [Pyrene] : [DMA] = 104 (M) : 0.27  102
(M) in DMSO. (a), (b), (c) and (d) are at 460 nm; (e) and (f) are at 600 nm; (g) and (h) reflect the long time base line stability of the lock-in output at 460 nm and 600 nm in
presence of light signal (u).

(B = BMSin2pft). BM is the peak of the alternating magnetic field
modulated at 14.1 Hz (f) and Eo is the Lock-in output locked at
the second harmonic (28.2 Hz) of the modulating signal. During
experiments BM is first set to zero and baseline is scanned for some
time (2 min), after which BM is switched to saturating strength
(200 G) and scanning is continued for another 2 to 4 min followed
by another baseline scan (BM = 0). Eo is proportional to the mag-
netic field induced change in the luminescence (Du). The graphs
do indicate that for low DMA concentration the MFE is essentially
negative at the blue end of the exciplex emission in DMSO,
whereas at the red end it is positive as expected from the known
mechanism. Table 1 shows the u and Du/u values for pyrene-
DMA exciplex system in DMSO and iso-dielectric mixture of pro-
pylene carbonate and N,N-dimethylformamide (DMF). We have
checked the possibility of formation of ground state complex be-
tween pyrene and DMA at the concentration ranges studied and
the result supports no ground state complex formation. At
440 nm or 420 nm we have observed no detectable MFE indicating
that the effect is not originating on pyrene luminescence. The data
clearly shows that at the red end of the exciplex emission the MFE
is always positive. However, at the blue end at low DMA concentra-
tion the effect is negative which changes to positive at high donor
concentration passing through an intermediate concentration
(6.0  102 M) where the effect is negligible immersed within
the noise of the detection system.
The negative MFE at the blue end at low donor concentration
can not be explained through a normal channel of singlet precursor
RIP generation from CT between 1Py⁄ and DMA. The observation

Table 1
u and (Du/u) values for Pyrene-DMA exciplex system. Concentration of Pyrene = 104 (M).
Solvent [DMA] (M) k = 460 nm k = 600 nm
u ( Du/u) u (Du/u)
DMSO (e = 46.45) 0.27  102 24 mV ()0.11% 0.68 mV (+)0.70%
6.00  102 5.6 mV (+)/() Negligible 0.42 mV (+)1.75%
19.8  102 6.0 mV (+)0.29% 0.40 mV (+)1.60%
Propylene carbonate + DMF mixture (e = 46.45) 0.27  102 18.8 mV ()0.05% 0.70 mV (+)0.74%
66 A.K. Jana et al. / Chemical Physics Letters 535 (2012) 63–68

Scheme 1. Kinetic model of the exciplex system at very high permittivity (e  47). A-Py; D-DMA; ½ASDFC -accepter, donor and solvent molecule assembly undergoing super-
exchange.

(1 A* + D)

U ISC
CT
T
R
Potential Energy (E)

(3 A* + D)
CT
(A- + D+)
Fluorescence
Exciplex

Excitation

(A + D)

Inter Radical Distance (A0 )

0 rCIP rg rST 10

Figure 3. Relative energy level diagram of radical ion pair (RIP) system at very high permittivity (e  47). rCIP-contact luminescent exciplex; rg-charge transfer distance; rST-
distance of singlet–triplet degeneracy. A-Py; D-DMA.

also indicates that in some way the ensemble of CIPs emitting at
blue end differs from that emitting at red end. To explain the neg-
ative MFE we presume a kinetic model depicted in Scheme 1. In
this model we have considered the formation of 3Py⁄ directly from
1
Py⁄ (kISC via vibrational relaxation along with spin–orbit coupling
for the multiplicity change i.e. coupled electron and nuclear mo-
tion). We further presume that at very high permittivity (e  47)
the RIP energy goes below the 3Py⁄ energy level. Figure 3 shows
a qualitative energy level diagram of the system drawn in light
of Ref. [14]. The RIP energy relative to the ground state is given by
E ¼ I  EA þ P  e20 =er
Where ‘I’ is the ionization energy of DMA (in ground state), ‘EA’ is the
electron affinity energy of 1Py⁄, P± is the total interaction energy of the
radical ions with the medium, e0 is the charge of electron and ‘r’ is the
inter-radical distance. The energy of the 1Py⁄ is on the order of 3.3 eV
with respect to the ground level and that of 3Py⁄ lies around 2.0 eV. It
is well known that in methanol (e  33) no negative MFE is observed
for all donor concentrations and thus the RIP energy must lie above
the 3Py⁄ energy. Considering an increased CT distance, rg  4 Å, in
DMSO (e  47) due to super-exchange the contribution from the Cou-
lomb-interaction term in Eq. (1) changes from 0.094 eV to 0.066 eV
only as the medium is changed from methanol to DMSO. It is thus
ð1Þ
very probable that simple Coulomb interaction cannot explain the
 A.K. Jana et al. / Chemical Physics Letters 535 (2012) 63–68
lowering of the RIP energy in DMSO and the effective form of the P±
term needs theoretical analysis. The basic CT mechanism is presently
well understood [24–28]. At CT distance the dipole and other higher
multi-pole moments of the solvent molecule play significant role and
electron tunneling occurs through solvent molecules. The long range
CT through super-exchange may eventually lead to the lowering of
the energy of the RIP state at rg (CT distance) bringing it below the
3
Py⁄ energy. This may also cause an increase in the solvent reorgani-
zation energy [29] leading to poor exciplex emission as indicated by
Figure 1. It is clear that at e > 47 the Coulomb energy term becomes
insignificant and the RIP energy effectively becomes flat at larger dis-
tance. Lowering of the RIP state below the 3Py⁄ energy will open the
channel for forming triplet precursor RIP (D) via CT from 3Py⁄ along
with the formation of singlet precursor RIP (B) from 1Py⁄ [30]. Accord-
ing to Scheme 1 at high donor concentration the quenching rate con-
stant kQS dominates the kISC and the formation of singlet precursor
RIP is favored. The MFE on exciplex (CIP) emission is positive.
Whereas at low donor concentration kQS decreases and kISC becomes
greater than kQS. The balance shifts towards generation of triplet pre-
cursor RIP and the MFE on exciplex luminescence is negative.
The second interesting feature of the observation is the wave-
length dependence of the negative MFE. At the red end of the emission
(k > 490 nm) the MFE is always positive. It has been established re-
cently that above e > 8 when solvent reorganization energy becomes
prominent the luminescent CIP exists in two different states, relaxed
and un-relaxed [23]. In the process of CT and exciplex (CIP) formation
some CIPs emit after complete solvent relaxation (Relaxed exciplex,
E), whereas there is an ensemble of CIPs which undergo emission
without waiting for complete solvent relaxation (Un-relaxed exci-
plex, F). The relaxed CIP being lower in energy emits in the longer
wavelength (k > 490 nm) whereas the un-relaxed type having higher
energy emits in the blue end of the spectrum (k  460 nm). We pre-
sume that at very high dielectric constant when the channel forming
the triplet precursor RIPs (D) is opened it effectively produces only
un-relaxed luminescent CIP through T?S conversion via hyper-fine
interaction (kHFI). The negative MFE is thus observed at blue end of
the spectrum only. At longer wavelength when characteristically only
the relaxed CIPs prevail the MFE is always positive at all values of
dielectric constant and donor concentrations.
We have checked the MFE at low donor concentration
(0.27x102 M) in DMF (e  37). At 600 nm the Du/u value is on
the order of 1.4%. But at 460 nm no MFE either negative or positive
has been observed. This indicates that as the RIP energy level rises,
the channel forming the triplet precursor RIP becomes less operative
and effectively concentration of singlet precursor RIP balances with
triplet precursor RIP so that no MFE at 460 nm for un-relaxed exci-
plexes is observed. In the extreme limit we have also measured the
MFE in propylene carbonate (e  65). In this case at 600 nm we have
observed positive MFE on the order of 0.86%. At 460 nm or 480 nm
however, there is no observable MFE. The un-relaxed CIP (U in
Figure 3) has lower activation barrier for dissociation and thus at
this value of dielectric constant effectively no un-relaxed species
exists.
Finally it is to be noted that at low DMA concentration the u
values of the exciplex at 460 nm is contaminated with the tail of
pyrene emission. The actual Du/u values in this condition will
be higher. Another point of interest is that the negative MFE at
460 nm for low DMA concentration in DMSO is almost double of
that in iso-dielectric propylene carbonate and DMF mixture. We
feel that the heavy atom effect [31,32] of Sulfur (S) in DMSO is
causing an enhancement of kISC and thus the negative MFE.
4. Conclusion
The Scheme 1, which provides an appropriate explanation of the
work presented, points to a few conceptual ideas as follows:
67
(1) At very high dielectric constant value of the medium when
remote charge transfer occurs, then super-exchange mecha-
nism acting in the system may effectively stabilize the RIP
energy level lowering it below the triplet energy level of
the excited species. This stabilization of RIP due to super-
exchange needs theoretical analysis.
(2) Under this situation simultaneous formation of singlet and
triplet precursor RIPs is favored which is very rare in litera-
ture, especially in case of unlinked donor, acceptor pair.
(3) The scheme strengthens the concept of relaxed and un-
relaxed exciplexes [23]. The possibility that exciplexes
(whether luminescent or not) may exist in two different
forms; one under complete solvent relaxation and another
undergoing no solvent relaxation becomes an important
issue. The un-relaxed exciplexes which do not wait for sol-
vent relaxation may show significant anisotropic character-
istic and may be of importance in nature. It has been
proposed that coherent anisotropic interaction (Zeeman
and hyperfine) induced spin evolution is the basic mecha-
nism of magneto-reception in migratory birds [33–36].
(4) Finally, the scheme points to the idea that triplet precursor
RIPs effectively generate only un-relaxed exciplexes. We will
try to give a plausible explanation of this proposal. The
explanation is based on the concept that the electron affinity
(EA) of 3Py⁄ is higher than 1Py⁄. A simple reasoning stands on
the fact that in case of CT in 1Py⁄ one electron from the
HOMO of the ground state DMA can be transferred to only
one orbital. But in case of 3Py⁄ as the two spins are identical,
there will be two orbitals where the electron from DMA can
be accommodated. Thus the CT rate in case of 3Py⁄ will be
higher than that in 1Py⁄. The fast CT in 3Py⁄ will definitely
lead to formation of triplet precursor RIPs predominantly
in un-relaxed state. Moreover as the DMA concentration is
very low and very remote CT is taking place the complete
solvent relaxation will also require some translational diffu-
sion and thus will be slower. In the mean time the HFI
induced ISC will continue to act on the triplet born precur-
sors and will produce singlet RIPs in a few nanoseconds
which will also predominantly be in the un-relaxed state.
On the other hand as the CT rate from 1Py⁄ is smaller, in case
of singlet born RIPs CT is likely to be a gradual process as the
solvent reorganization follows and induces the overlap of
the interacting molecular orbitals [37]. This will lead to for-
mation of both relaxed and un-relaxed RIPs. The excess
energy of the singlet born RIPs is effectively get dissipated
in the bath because of the slow CT in the form of solvent
reorganization, whereas in case of triplet born RIPs the fast
CT reduces the extent of solvent reorganization and dissipa-
tion to bath is reduced.
In summary, to explain the negative MFE at very high value of
permittivity we have postulated the lowering of RIP energy level
through super-exchange and simultaneous CT from 1Py⁄ and 3Py⁄
forming singlet as well as triplet precursor RIPs. To explain the
wavelength dependence of negative MFE we have presumed that
triplet precursor RIPs effectively generate only un-relaxed CIP. In
conclusion, the work describes interesting findings and at the same
time triggers many questions unanswered. Though the observation
is made in specific pyrene-DMA exciplex system, we feel the basic
mechanism can be extended to general RIP systems. It is to be
noted that in nature the basic charge transfer phenomenon occurs
in an environment having large dielectric constant. As for example,
environment in a living cell is mainly made of water in free and
bound state. It is possible that many important charge transfer pro-
cesses occur in the mobile region of the water where dielectric
constant can be high. The role of radical pair mechanism in
68 A.K. Jana et al. / Chemical Physics Letters 535 (2012) 63–68

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