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The complex between molecular oxygen and an

organic molecule: modeling optical transitions to
Cite this: Phys. Chem. Chem. Phys.,
2021, 23, 15038 the intermolecular charge-transfer state†
Frederik Thorning, Kris Strunge, Frank Jensen * and Peter R. Ogilby *

Received 21st April 2021,
Accepted 28th June 2021
DOI: 10.1039/d1cp01738a
rsc.li/pccp
The collision complex between the ground electronic state of an organic molecule, M, and ground state
oxygen, O2(X3Sg), can absorb light to produce an intermolecular charge transfer (CT) state, often
represented simply as the M radical cation, M+ , paired with the superoxide radical anion, O2 . Aspects
of this transition have been the subject of numerous studies for B70 years, many of which address
fundamental concepts in chemistry and physics. We now examine the extent to which the combination
of Molecular Dynamics simulations and electronic structure response methods can model transitions to
the toluene–O2 CT state. To account for the experimental spectra, we consider (a) the distribution of
toluene–O2 geometries that contribute to the transitions, (b) a quantitative description of intermolecular
CT, and (c) oxygen-induced local transitions in toluene that complement the CT transitions, specifically
transitions that populate toluene triplet states. We find that the latter oxygen-induced local transitions
play a prominent role on the long wavelength side of the spectrum commonly attributed to the
intermolecular CT transition. Our calculations provide a new perspective on the seminal discussion
between R. S. Mulliken and D. F. Evans on the nature of O2-dependent transitions in organic molecules,
and bode well for modeling transitions to excited states with CT character in noncovalent weakly-
bonded molecular complexes.

Introduction the O2(a1Dg) excitation energy, continue to provide a unique

Interactions between an organic molecule, M, and molecular
oxygen have played a key role in the study of noncovalent
complexes for B70 years.1–4 This work has complemented
related studies on noncovalent interactions between benzene,
in particular, and molecular iodine.1,3,5
Much of the work on M and O2 has focused on cases where
one of the interacting partners is in an excited electronic
state.2,6,7 For example, the quenching of a triplet state organic
molecule, 3M1, by ground state oxygen, O2(X3Sg), with energy
transfer to produce singlet molecular oxygen, O2(a1Dg), has
provided insight into a variety of fundamental chemical and
physical principles (e.g., factors within the M–O2 complex that
influence changes in electron spin angular momentum).6,8–12
Likewise, ascertaining the roles played by the ground state of an
organic molecule, 1M0, to induce the forbidden O2(a1Dg) -
O2(X3Sg) transition and then, independently, act as a sink for
Chemistry Department, Aarhus University, DK-8000, Aarhus, Denmark.
E-mail: frj@chem.au.dk, progilby@chem.au.dk
† Electronic supplementary information (ESI) available: Details and results from
TD-DFT calculations; parameters for the AMOEBA polarizable force field; details
of the MD simulation; MD-based spectra calculated using different sampling
methods. See DOI: 10.1039/d1cp01738a
exercise in the study of intermolecular electronic-to-vibrational
energy transfer.13,14
Studies of the interaction between 1M0 and O2(X3Sg) are
challenging because this ground state complex is very weakly
bound,15–17 which is consistent with Mulliken’s moniker of a
‘‘collision complex’’.18 Nevertheless, such studies are facilitated
by a distinctive optical transition, first observed as a red shift in
the onset of light absorption in liquid solutions of M upon
the introduction of O2.18–20 After much discussion, a key
component of this absorption was assigned to a transition
from a 1M0–O2(X3Sg) collision complex to an intermolecular
charge transfer, CT, state.18 Although the latter is often represented
as a pair of radical ions, M+ O2 , implying complete electron
transfer (Fig. 1), it is understood that a description involving
partial charge transfer may be more appropriate.1,18 In some
cases, the absorption spectrum due to 1M0 alone can be
subtracted to indicate that the M–O2 CT transition is a broad
structureless band,15,17,21 which is consistent with a weakly
bound ground state complex to which many different 1M0 and
O2(X3Sg) orientations contribute. The effective concentration
of this complex, which influences the intensity of the CT
transition, is reflected in the magnitude of the equilibrium
constant for M–O2 formation from M and O2.

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Fig. 1 Approximate relative energies of states in the complex between
oxygen and an organic molecule xMy (the superscript x denotes electron
spin and the subscript y denotes either the ground state, 0, or the first
excited state, 1). Both spin-allowed one- and two-photon excitation to the
non-equilibrated Franck–Condon, FC, triplet CT state are shown (blue and
red arrows, respectively). The energy of the CT state depends on the
ionization potential of M (i.e., the stability of the M radical cation). In liquids,
the energy of the solvent-equilibrated, SE, CT state also depends on
the dielectric properties of M (gray bar). The green arrows illustrate one
non-radiative process that results in the formation of O2(a1Dg).
Other transitions in the M–O2 complex can play an appreci-
able role in the same spectral region as the M–O2 CT transition.
These transitions reflect the way one of the interacting partners
can perturb formally forbidden local transitions in the other
partner. Thus, perturbation by M can increase the probability of
the forbidden UV Herzberg transitions that populate highly
excited states of oxygen (i.e., A3Su+, c1Su, and A 0 3Du).4,22
However, this phenomenon is perhaps most visibly exemplified
in the spectrum of liquid benzene where O2-induced 1M0 - 3M1
vibronic bands are clearly superimposed onto the broad CT
band.18,20,23,24 Distinguishing between these different transitions
was a key issue in the seminal discussion between R. S. Mulliken
and D. F. Evans on the nature of O2-dependent transitions in
organic molecules,18,25 with Mulliken focusing on the role of the
CT state and Evans on the magnetic and spin properties of
O2(X3Sg).
For common organic molecules, the ground state M–O2
complex has a net triplet spin reflecting the combination of a
singlet organic component, 1M0, and triplet oxygen, O2(X3Sg).
In contrast, the combination of two triplet states in the
3
M1–O2(X3Sg) complex yields singlet, triplet, and quintet spin
states, which are nearly degenerate in the weakly interacting
limit. In this way, the oxygen-induced 1M0 - 3M1 transition is
readily seen as a spin-allowed process between M–O2 triplet
states. The Franck–Condon CT state will likewise have triplet
spin. Subsequent intersystem crossing to a singlet CT state
coupled with nuclear relaxation (i.e., a solvent-equilibrated
state in liquids) can precede the formation of other states of
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the M–O2 complex.20,26–28 The production of O2(a1Dg) upon
irradiation into the M–O2 CT band has been of particular
interest in this regard (Fig. 1).20,26,29 This latter approach to
produce O2(a1Dg) complements the 3M1-sensitized production
of O2(a1Dg), and provides mechanistic insight for studies of
transitions between different states of the M–O2 complex.26,27
The available data are all consistent with the long-held under-
standing that mixing of the M–O2 CT state with other states of
the M–O2 complex plays a significant role in the photophysics of
oxygenated systems.2,6,7,9,10,26,30 For example, state mixing between
the CT state and the comparatively low-energy 1M0–O2(a1Dg) and
1
M0–O2(X3Sg) states facilitates the formally-forbidden transition
between O2(a1Dg) and O2(X3Sg).6,14,31,32
We have shown that the M–O2 CT state can also be populated
via two-photon absorption using visible light, which likewise
results in the production of an appreciable amount of O2(a1Dg)
(Fig. 1).29 Although this observation has ramifications for a
range of experimental studies, it also provides useful fodder
for theoretical and computational studies of optical transitions
in noncovalent complexes.
Computational modeling of linear and nonlinear optical transi-
tions has received much attention over the years.33 Appreciable
advantages are realized with the use of response methods, which
avoid sum-over-states approaches and errors that can arise if
mixing with a particular excited state is not considered.34–37
Response methods implicitly consider all excited states, with
the principal requirement being an accurate ground state wave
function.34,38 Response methods based on Time Dependent
Density Functional Theory (TD-DFT) are popular due to their
computational efficiency,39 while corresponding methods based
on coupled cluster reference wave functions provide a hierarchy
of systematically more accurate results.2,37,40–42
When dealing with transitions to states with significant CT
character, TD-DFT often significantly underestimates excitation
energies due to the charge being over-delocalized by typical
exchange–correlation functionals,34,43 and calculated absorption
cross sections can be erroneous due to an incorrect assessment of
the excited state dipole moment.40 One approach to address this
problem involves using so-called range-separated functionals
where the DFT exchange functional is gradually modified to
Hartree–Fock (HF) exchange as the interelectronic distance
increases.44 The interpolation between these two extremes is
usually done by the error function with a range-separation
parameter o that determines the distance where the transition
from DFT exchange to HF exchange occurs.44,45 The o para-
meter is often optimized to reproduce reference data for intra-
molecular CT states.45,46
Computational modeling of excitation energies in inter-
molecular complexes with CT character is a problem that is
currently being addressed on a number of fronts.43,47–51 In the
present study, we employ TD-DFT and Equation-of-Motion
Coupled-Cluster (EOM-CCSD)41 methods to model transitions
to the CT state in the M–O2 system (Fig. 1), using toluene as the
molecule M. This problem is not only influenced by the range-
separation parameter o in the TD-DFT approach, but one must
also account for the shallow 1M0–O2(X3Sg) potential surface.
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The latter implies that transitions from a plethora of 1M0 and
O2(X3Sg) geometries must be considered and suitably averaged.
Success with these calculations, as judged by comparison to
experimental data, allows us to comment on the magnitude of
the equilibrium constant for the formation of the 1M0–O2(X3Sg)
‘‘collision’’ complex, a problem that has likewise challenged the
community for many years.15–18
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Results and discussion
M–O2 CT absorption spectrum
Experimental data. To our knowledge, an M–O2 CT spectrum
has only been recorded for the benzene–O2 complex in the gas
phase, achieved by subtracting the spectrum of benzene itself
from the data recorded under oxygenated conditions.15,17,21
The resultant broad and structureless band has a maximum
at B215 nm.15,17,21 Analogous data obtained from frozen
matrices at 10 K yield a band maximum at B235 nm for the
benzene–O2 CT band and B245 nm for the toluene–O2 CT
band.52 Although the observed red shift in going from benzene
to toluene is arguably consistent with the expected change in
the energy of the CT state (i.e., the toluene radical cation is
more stable), the band maxima of these low temperature data
likely reflect discrete M and O2 orientations and intermolecular
distances that are only part of the distribution of M and O2
geometries that characterize gas and liquid phase data.
In liquid solutions of M, absorption attributed to the M–O2
CT transition appears as a bathochromic shift to the absorption
onset of M itself (i.e., one observes a long-wavelength ‘‘tail’’ on
the absorption spectrum of M).18,20,26 Measuring the full CT
spectrum in this case is challenging since local transitions of
the highly concentrated M dominate and generally saturate the
spectrometer, prohibiting subtraction to yield the CT band. To
our knowledge, the M–O2 CT spectrum in liquid M has never
been recorded in the same manner as the gas phase spectrum
discussed above. Available liquid phase data for the toluene–O2
system only reveal the tail of the absorption spectrum, which
extends out to wavelengths as long as B370 nm.20
On the basis of these data, one criterion of computational
success is to model a broad toluene–O2 CT absorption band
with a maximum at B215–220 nm and a tail that extends out to
B370 nm, with the added goal of providing molecular insight
into the origin of this spectrum.
Preliminary calculations: structures and energies. As a starting
point, and inspired by previous work on related systems,12,30,53–55
we chose a few discrete geometries for the toluene–O2 complex.
Energy optimization of these geometries at the oB97X-D/6-31G(d)
level yielded the four structures shown in Fig. 2. Using TD-DFT
with the oB97X-D range-separated functional optimized for
intramolecular CT excitations (o = 0.2 bohr1),46,56 we ascertained
that the lowest energy toluene–O2 CT transition at B310 nm was
associated with structure B in Fig. 2 (see ESI† for details). Although
the CT transition wavelengths for the other 3 structures in
Fig. 2 (B250–260 nm) are blue-shifted relative to this value of
310 nm, they nevertheless still occur at wavelengths longer than
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Fig. 2 Four geometry-optimized structures of the ground state toluene–
O2 complex used for preliminary calculations of the M–O2 CT spectrum.
the B215 nm expected from experimental data. If we assume
that the toluene–O2 structures in Fig. 2 are representative of
ground state collision complexes, then this deviation from the
experimental data suggests limitations of the DFT model for
intermolecular charge-transfer excitations (vide supra).
For electronic transitions in a non-centrosymmetric system,
such as the M–O2 complex, selection rules indicate that the final
states populated in a one-photon process should also be populated
in a two-photon process.57 Assuming that the abovementioned
limitation of DFT will apply equally to one- and two-photon
calculations, we indeed observe that the respective spectra are
the same (Fig. S2, ESI†). Limiting ourselves to the electric dipole
term of the multipole expansion, we calculate a one-photon molar
absorption coefficient of B2000–4000 M1 cm1 and a two-
photon cross section of B5–8 GM, both at the maxima of the
respective toluene–O2 absorption bands.
Tools to accurately and efficiently model the toluene–O2 CT
transition
Tuning the range-separation parameter x. The preliminary
calculations described above suggest that modification of the
range-separation parameter o may be required for modeling
intermolecular CT transitions.
Kozma, et al.58 have investigated the performance of differ-
ent coupled cluster methods for predicting excitation energies
of intermolecular CT transitions in complexes of two organic
molecules. Taking the CCSDT-3/cc-pVDZ results of Kozma,
et al. as our benchmark, we calculated CT excitation energies
for 10 of their intermolecular transitions using TD-DFT with the
oB97X-D functional and the aug-pcseg-259 basis set. For these
10 transitions, using the standard value of o optimized for
intramolecular CT (0.2 bohr1) yields a mean absolute deviation
of B2 eV between the coupled cluster and DFT results, a value
that far exceeds what is acceptable for computational assess-
ment of a CT transition.46 Fig. 3 shows the mean absolute
deviation for these 10 CT transitions as a function of different
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Fig. 3 Plot of the mean absolute deviation between intermolecular CT
state energies for 10 different CT states between two organic molecules
computed using a high-level coupled cluster approach (CCSDT-3/cc-pVDZ)58
and a TD-DFT approach (oB97X-D/aug-pcseg-2) as a function of the range-
separation parameter o. The data show that a range separation parameter of
0.5 bohr1 is most appropriate for use when dealing with intermolecular CT
states. The error bars represent the standard deviation on the mean.
values of o, covering the range from 0.1 to 1.0 bohr1. Increasing
o to 0.5 bohr1 reduces the deviation to 0.4 eV, which is
comparable to the accuracy for valence excitations,60–63 and this
value may be suitable for modelling intermolecular CT states.
Kozma, et al.58 considered complexes of organic molecules
with ground and CT states that have singlet spin, whereas the M–O2
complex has ground and Franck–Condon CT states with net triplet
spin (Fig. 1). Because DFT often has problems calculating accurate
energy differences of different spin states, it does not automatically
follow that the calibration in Fig. 3 carries over to the M–O2 system.
Thus, as outlined further below, we have chosen to compare
TD-DFT results with those obtained using EOM-CCSD methods.
MD simulation for the M–O2 ground state. Rather than
working with a given structure for the toluene–O2 ground state
complex, albeit with precedence and energy-optimization (vide
supra), the shallow ground state potential surface implies that a
large number of toluene–O2 geometries will contribute to both
CT transitions and to O2-perturbed local transitions in toluene
at ambient temperatures. Investigating these geometry effects
requires a statistical sampling of possible structures and we
have chosen to rely on Molecular Dynamics (MD) simulations
to capture a more statistically accurate picture of the ground
state toluene–O2 structures.
Although force field parameters for toluene are available,64
parameters for molecular oxygen, to our knowledge, are not. With
the intent of using the AMOEBA Polarizable Force Field,64 we
derived parameters from information on the O–O bond length
and vibrational frequency,65 van der Waals interaction,66 the static
molecular polarizability,67 and the molecular quadrupole moment68
(details are provided in the ESI†). We generated a cubic simulation
box with 100 toluene molecules and one oxygen molecule using
Packmol69 and used the Tinker 8 software package70 to perform a
10 ns MD simulation under NVT conditions (see ESI† for details).
To establish a statistically relevant number of independent
toluene–O2 structures, we argue that a ‘‘snapshot’’ of the toluene–
O2 ensemble taken every 100 ps should be sufficient. Specifically,
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expected rotational correlation times and radial diffusion
distances,71,72 coupled with the anticipated short lifetime of
the collision complex,18 all indicate that structures separated by
100 ps should not be correlated, leading to 100 independent
snapshots extracted from the 10 ns simulation.
We used three approaches to analyze the simulation:
(a) extracting a snapshot every 100 ps, we identified the one
toluene molecule that is closest to oxygen (i.e., the shortest
distance between an atom in toluene and one of the oxygen
atoms), leaving us with 100 different 1 : 1 complexes arguably
representatively placed on the toluene–O2 potential surface.
(b) Using the same 100 snapshots, we identified the two toluene
molecules that were closest to oxygen, leaving us with 100
different complexes with 2 : 1 stoichiometry. (c) For snapshots
separated by 1 ps, we calculated the distance between the O2
center-of-mass and the toluene center-of-mass for every toluene
molecule (com-to-com distance), and selected the 1 : 1 complex
with the shortest com-to-com distance. For a 10 ns simulation
window, this yields a distribution of com-to-com distances for
9900 structures that covers the range B3–6 Å. For each 100 ps
window, we then selected one snapshot such that the total
distribution of com-to-com distances for 9900 structures was
reproduced as well as possible using 99 structures. With any of
these sampling methods, if oxygen is situated near the edge of the
simulated box, the nearest toluene molecule might be located in
the adjacent box. We account for this by redefining the boundaries
of the box such that oxygen is placed in the center.
Details of these sampling approaches are given in the ESI.†
Modeling M–O2 CT excitations
TD-DFT computations. For each of the three sampling methods
used to assess the MD simulation, we calculated excitation
energies and the associated oscillator strengths for the toluene–
O2 structures using TD-DFT with the oB97X-D functional and the
range-separation factor of 0.5 bohr1 using the aug-pcseg-1 basis
set.59 Each of these calculations resulted in a spectrum showing
discrete transitions (i.e., a ‘‘stick’’ spectrum, see ESI†). A similar
computation was performed for toluene in the absence of oxygen,
using the molecular geometry in the complex. To emulate
experimental results, we generated structureless band spectra
by broadening each discrete transition with a Gaussian function
(s width of 1000 cm1) and adding the results for all 100
snapshots. We then subtracted the toluene spectrum from the
spectrum of oxygenated toluene to show the behavior unique to
the toluene–O2 complex. Irrespective of the sampling method
used to assess the MD simulation, the resultant spectra show an
absorption band maximum of B215 nm (Fig. 4) which appears
to meet our criterion of computational success based on the
expectation from experimental data (vide supra). The observation
that complexes of 1 : 1 and 2 : 1 stoichiometry yield essentially the
same result indicates that the molecule closest to oxygen is most
important in defining the M–O2 spectrum. This conclusion should
facilitate attempts to correlate gas and solution phase data.
Weak point in the TD-DFT computations. Irrespective of the
MD-derived toluene–O2 geometries used, our TD-DFT computations
always revealed a separate group of appreciably red-shifted
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Fig. 4 TD-DFT computed absorption spectrum for the toluene–O2 complex
obtained by subtracting the computed spectrum for toluene from the
computed spectrum for toluene containing oxygen (see text). Computations
were performed using a range-separation parameter o of 0.5 bohr1 and the
data shown here were obtained for a 1 : 1 stoichiometry of toluene to oxygen.
The band maximum occurs at B215 nm. The inset shows an expanded view
of the transitions over the range 350–700 nm, with a band maximum at
B500 nm (note the change of intensity scale). Corresponding spectra
obtained when using the other two methods to assess the MD simulation
are similar and are shown in the ESI.†
transitions (B500 nm) with low oscillator strengths (o0.0001,
see inset of Fig. 4 and Fig. S4, ESI†). This part of the calculated
spectrum is readily assigned to local transitions in toluene that
are perturbed by oxygen, in particular 1M0 - 3M1 transitions.
In our nonrelativistic approximation, these singlet–triplet
transitions in isolated toluene are forbidden. However, as
mentioned earlier, a transition from the triplet ground state
complex, 3(1M0–O2(X3Sg)), to the triplet component of the
( M1–O2(X3Sg)) excited state is allowed. From experimental
1,3,5 3
data, the 1M0 (v = 0) - 3M1 (v = 0) transition in toluene occurs
at 346 nm,73 which is appreciably blue-shifted from the
B500 nm band shown in the inset of Fig. 4 obtained using
the TD-DFT calculations.
To help assess this observation, we performed coupled cluster
calculations on the MD-derived 1 : 1 toluene–O2 structures (EOM-
CCSD/aug-cc-pVDZ). In contrast to the TD-DFT calculations, the
EOM-CCSD results do not place these transitions at such low
energies (Fig. 5A). Rather, they better represent experimental data
where a ‘‘tail’’ extends out to B370 nm on the long-wavelength
side of the toluene–O2 absorption band.20 Moreover, the EOM-
CCSD results show two distinct groupings of long-wavelength
transitions (insets in Fig. 5A). On the basis of our preceding
discussion, we assign the band that occurs over the range B310–
350 nm to transitions that populate the lowest energy triplet state
in toluene, 3M1, which is in good agreement with the experimen-
tally observed band at 346 nm. By extension, we assign the band
that occurs over the range B240–275 nm to transitions that
populate higher energy triplet states (e.g., 3M2). Although the
accuracy of calculating oscillator strengths of such weak transitions
is limited, our results model experimental data well. Moreover, it is
clear that the band assigned to the 1M0 - 3M2 transition is
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Fig. 5 (A) Coupled cluster computed spectrum for the toluene–O2
complex obtained using a 1 : 1 stoichiometry of toluene to oxygen with the
same structures used for the calculation in Fig. 4. The distinct grouping of the
red-shifted transitions, amplified in the insets, reflects oxygen-induced
transitions to the local triplet states of toluene: 3M1 and 3M2 (see text).
(B) For discrete EOM-CCSD computed transitions in the toluene–O2
complex (see text), the plot indicates the extent of charge displacement.
Many transitions over the range B200–230 nm have appreciable charge
displacement which is consistent with intermolecular CT, whereas the
transitions at longer wavelengths are consistent with localized oxygen-
induced transitions in toluene in which little charge displacement occurs.
more intense than the band assigned to the 1M0 - 3M1
transition. In part, this could reflect the reasonable expectation
that the higher energy 1,3,5(3M2–O2(X3Sg)) states will more
readily mix with both the M–O2 CT state and singlet excited
states of toluene to which transitions are more allowed.
The band maximum obtained from the EOM-CCSD spectrum
occurs at B205 nm, which is slightly blue shifted relative to the
band maximum obtained in the TD-DFT calculation. Asserting
that our coupled cluster results are accurate, this deviation of
B0.3 eV is well within the expected error of a DFT calculation.60–63
However, given our approach to obtain these broadened spectra
(vide supra), the inherent uncertainty associated with subtracting
our modeled toluene spectrum from the spectrum of the toluene–
O2 complex could also easily account for this difference in the
band maxima.
The results shown in Fig. 4 and 5A clearly point to a limiting
feature of the TD-DFT approach. With an o value of 0.2 bohr1
appropriate to model intramolecular transitions in toluene,
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Fig. 6 Illustration of how the TD-DFT calculated wavelength of two
selected transitions in a 1 : 1 toluene–O2 complex varies with the range-
separation parameter o used in the calculation. When using o =
0.5 bohr1, the TD-DFT calculation for a transition to the intermolecular
CT state (solid blue line) comes close to the transition wavelength
calculated using EOM-CCSD for the same toluene–O2 geometry (dashed
blue line). However, relative to this EOM-CCSD result, the TD-DFT
calculation shows a large redshift as o is decreased to a value commonly
used for intramolecular transitions, 0.2 bohr1. When using o = 0.2 bohr1,
the TD-DFT calculation for an oxygen-induced transition to the triplet state
of toluene (solid red line), exemplifying a local intramolecular transition,
yields a transition wavelength close to the EOM-CCSD result (dashed red
line). However, the TD-DFT result likewise shows a large redshift relative to
the EOM-CCSD result upon increasing o to the value of 0.5 bohr1 suitable
for an intermolecular transition.
TD-DFT does not properly model intermolecular toluene-to-oxygen
CT transitions. With an o value of 0.5 bohr1 appropriate to model
intermolecular toluene-to-oxygen CT transitions, TD-DFT does
not properly model intramolecular transitions in toluene with
intensities perturbed by oxygen. We illustrate this phenomenon
in Fig. 6.
Thus, TD-DFT cannot accurately model the wide range of
optical transitions that characterize the toluene-oxygen collision
complex. Although changing the o value presents a valuable tool
for TD-DFT studies of pure CT transitions, accurate predictions
of a wide range of transitions in a given molecular system
requires more sophisticated computational methods. Indeed,
our results show that coupled cluster methods provide a more
balanced description of both intermolecular CT transitions and
O2-perturbed local transitions in toluene.
Exploring features of the toluene–O2 absorption band
Effect of intermolecular distance. Using the EOM-CCSD
method, and limiting ourselves to the complex with geometry B
in Fig. 2, we examined the effect of changing the intermolecular
distance between toluene and oxygen, as measured from the
center of mass in oxygen to the center of the aromatic system in
toluene. With an increase in the intermolecular distance, we find
that (a) the energy of the CT transition increases, as reflected in a
systematic blue shift of the absorption band, and (b) the transition
oscillator strength decreases (Fig. 7). At an intermolecular
separation distance of 4 Å, the spectrum is nearly indistinguishable
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Fig. 7 Spectra of the toluene–O2 complex calculated at the EOM-CCSD/
aug-cc-pVDZ level of theory, with the intermolecular distance ranging from
2.75 to 4.00 Å. The inset shows an expanded view of the band assigned to the
oxygen perturbed 1M0 - 3M1 transition. Oxygen does not appreciably perturb
toluene at intermolecular distances greater than B4 Å (i.e., over this wave-
length range, the spectra are superimposable; data not shown).
from the spectrum of pure toluene, clearly showing the B band at
around 250 nm and the tail of the K band just above 200 nm.74
These observations are consistent with expectation, and can be
ascribed to a decrease in the overlap between electron donor and
acceptor wave functions in Mulliken’s theory on CT in molecular
complexes.1 The corollary to this is that the exact position of the
calculated CT band maximum may depend on details in the force
field parametrization used in the MD simulation to obtain the
M–O2 geometries. Complementary intermolecular distance plots,
obtained using TD-DFT for both one- and two-photon transitions,
show the same general trend (see ESI†). However, as perhaps
expected, the one- and two-photon transition probabilities scale
differently with the M and O2 intermolecular distance.
For the EOM-CCSD results shown in Fig. 7, the intensity
of the band at B330 nm assigned to the oxygen perturbed
1
M0 - 3M1 transition decreases rapidly with increasing inter-
molecular distance, while the transition wavelength remains
almost unchanged. Again, this is consistent with expectation:
the perturbation of forbidden local transitions in an organic
molecule by oxygen, and vice versa, primarily influences transition
probabilities, not excitation energies.13
As a corollary to these distance-dependent changes in the
spectra, we also find that, for a given intermolecular distance in
structure B of Fig. 2, the spectrum changes as oxygen is rotated
relative to the toluene axis defined by the pendant methyl group
(see ESI†). Similar rotationally-mediated transition probabil-
ities have been posited for other intermolecular complexes.50,55
Assessing charge displacement. In our discussion, we imply
that three types of transitions contribute to what has traditionally
been dubbed the M–O2 CT band. The intense peak at shorter
wavelengths consists of transitions with appreciable CT character
along with toluene-induced transitions to highly excited states of
oxygen in which little charge displacement occurs. The absorption
tail at longer wavelengths reflects oxygen-assisted local transitions
in toluene in which little charge displacement likewise occurs.
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While no unique method exists for quantifying the CT
character of a transition, we used the index proposed by Bahers,
et al.75 to express the extent of charge displacement in the final
state populated by an optical excitation. To this end, and using
the EOM-CCSD results, we first removed discrete transitions
from the toluene–O2 spectrum that also appeared in the toluene
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spectrum. It is assumed that transitions in the toluene–O2
spectrum closest in wavelength to those in the toluene spectrum
are the same (i.e., spin-allowed singlet–singlet local transitions
in toluene). Although 1M0 - 3Mn transitions in the oxygen-free
toluene spectrum have exactly zero intensity, they become
spin-allowed and gain intensity upon perturbation by oxygen
(vide supra). As a result, we retain transitions unique to the
toluene–O2 complex.
In Fig. 5B, we plot the distance between the barycenters of
the density increment and depletion due to the excitation (i.e.,
the CT index of Bahers, et al.75) against the excitation wavelength
of the toluene–O2 transitions. As shown, we find that transitions
at wavelengths longer than 240 nm show effectively no displace-
ment of charge, whereas many of the transitions at wavelengths
shorter than 240 nm show appreciable charge displacement. As
such, the former are consistent with a localized excited state of
toluene.
Revisiting the Mulliken–Evans debate. Our calculations on
the toluene–O2 complex indicate that oxygen-induced local
transitions in toluene play an appreciable role on the long
wavelength side of the absorption spectrum commonly attributed
to the intermolecular CT transition. This is consistent with
the phenomenon most visibly exemplified in the experimental
spectrum of oxygenated liquid benzene where O2-induced
1
M0 - 3M1 vibronic bands are clearly superimposed onto the
broad CT band.20,23,24 Based on this observation for benzene
and our calculations on the toluene–O2 complex, it is reason-
able to assign similar, albeit very weak, ‘‘bumps’’ on the
long wavelength tail of the experimental toluene spectrum to
O2-induced 1M0 - 3M1 vibronic bands.20 As such, our results
support points made by both Mulliken and Evans in their
discussion on the nature of O2-dependent transitions in
organic molecules.18,25
This wavelength-dependent superposition of different M–O2
transitions has also been discussed in the context of experi-
ments wherein O2(a1Dg) is produced upon irradiation into the
M–O2 absorption band (Fig. 1).20,26,29 Although there is strong
evidence to indicate that O2(a1Dg) can indeed be produced upon
population of the M–O2 CT state (Fig. 1),20,26,76 it is likely that,
for some molecules M under some experimental conditions, a
fraction of the O2(a1Dg) produced is a consequence of an oxygen-
induced 1M0 - 3M1 transition followed by the 3M1 sensitized
production of O2(a1Dg).29
The equilibrium constant for ground state complex formation
A key limitation in experimental studies of optical transitions of
weakly bound intermolecular complexes is that, in the Lambert–
Beer expression, one can only directly determine the product of
the absorption coefficient with the concentration of the ground
state complex. The latter is often represented in terms of the
15044 | Phys. Chem. Chem. Phys., 2021, 23, 15038–15048
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Paper
Fig. 8 Illustration of key parameters that influence the M–O2 CT absorp-
tion band, where ecom refers to the molar absorption coefficient of the
transition to the CT state, and Kcom refers to the equilibrium constant for
ground state complex formation.
equilibrium constant for complex formation, Kcom, as shown in
eqn (1) and Fig. 8 for a generic M–O2 complex.


M  O2 X3 Sg
Kcom ¼ 
 (1)
½M O2 X3 Sg
For one-photon transitions, it is common to rely on the Benesi-
Hildebrand77 or Drago-Rose78 treatments to separate Kcom from the
molar absorption coefficient of the complex, ecom. Both techniques
exploit changes in sample absorbance as a function of a change in
the concentration of one of the interacting components. The
accuracy of these treatments, however, decreases appreciably
for weak complexes,79–81 and certainly for ‘‘collision’’ com-
plexes, of which the M–O2 complex is an excellent example.15
When considering eqn (1) and the common approach of
using oxygen-saturated solutions of neat M, the concentration
of M (typically B10 M, or greater) far exceeds the concentration of
oxygen (typically B10 mM, or less82). This inequality mirrors what
is generally applied in the Benesi–Hildebrand and Drago-Rose
treatments.15,77,78 In their 1960 paper on liquid solvents,
Tsubomura and Mulliken estimated ecom assuming that all
dissolved oxygen formed the ground state M–O2 complex.18 In
a recent paper on the two-photon excitation of the M–O2 CT
transition, the magnitude of the absorption cross section was
estimated assuming that only 1% of the dissolved oxygen
formed the ground state M–O2 complex.29 In both cases, errors
on the absorption coefficients are large, reflecting the large uncer-
tainty in the concentration of the ground state M–O2 complex.
With these limitations in mind, a way to independently
assess either ecom or Kcom would be a useful contribution.
Using computational results to quantify Kcom
With our computational model, one does not need to know the
concentration of the ground state M–O2 complex to quantify
transition probabilities. Our present results thus facilitate an
independent assessment of Kcom for the toluene and oxygen
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Fig. 9 For the toluene–O2 spectrum calculated using 100 1 : 1 complexes
obtained from an MD simulation, the plot shows the fraction of the
spectrum that is recovered as a function of the number of geometries
incorporated. The dashed line shows that B99% of the spectrum is
recovered when 54 of the 100 geometries are used.
system. Given the inherent errors, we assume that this exercise
is equally applicable to both liquid and gas phase systems.
To use our MD results in this regard, we exploit the general
ergodic theorem from statistical mechanics paraphrased to say
that considering one molecule for a long time is equivalent to
considering many molecules at one time.83 For each method
of assessing our MD simulation (vide supra), we obtain
100 different toluene–O2 structures within the 10 ns simulation
window. We can then determine what fraction of these structures
must be considered to account for a given percentage of the
toluene–O2 spectrum, as quantified by the sum of the respective
oscillator strengths. To this end, we employ the same EOM-CCSD/
aug-cc-pVDZ spectrum of discrete transitions used to obtain the
data shown in Fig. 5. Given the relative intensities of the toluene–O2
transitions (Fig. 5A), this exercise principally reflects a combination
of the transition to the CT state as illustrated in Fig. 8 along with
toluene-induced transitions to higher excited states of oxygen. We
find that 43 of the structures account for B95% of the spectrum,
and 54 of the structures account for B99% of the spectrum (Fig. 9).
This indicates that about half of the oxygen molecules present in a
statistically viable ensemble of toluene and oxygen contribute to the
light-absorbing collision complex at any given time.
For an experiment in which [M] c [O2], we can correlate this
fraction to the ratio [M–O2]/[O2] in eqn (1) and, with [M] = 9.45 M
for toluene, this yields an equilibrium constant Kcom of
B0.1 M1. This value of Kcom is appreciably smaller than the value
of B3–6 M1 estimated from a Drago-Rose treatment of benzene
data,15 reinforcing the fact that the latter experimental approach is
indeed error prone for weakly bound collision complexes.79–81
Conclusions
The combination of molecular dynamics simulations and electronic
structure response methods is an approach to accurately model
optical transitions from weakly bound M–O2 collision complexes,
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PCCP
as exemplified by our present results on the toluene–O2 complex.
Our calculations show that, while the peak of what is commonly
viewed as an intermolecular M–O2 CT band indeed has sub-
stantial CT character, the long wavelength tail of the band is
better ascribed to oxygen-assisted local transitions to triplet states
of M. In this way, we achieve a compromise in the classic debate
between R. S. Mulliken and D. F. Evans on the nature of oxygen-
dependent transitions in organic molecules in which Mulliken
championed the importance of the CT state and Evans the spin
properties of O2(X3Sg). Our results thus indicate that, in some
cases, claims of O2(a1Dg) production from the M–O2 CT state may, in
fact, reflect O2(a1Dg) production via an oxygen-induced 1M0 - 3M1
transition followed by the 3M1 sensitized production of O2(a1Dg).
Through our M–O2 study, we highlight a weak point of using
time-dependent density functional theory, TD-DFT, to model
systems in which both local transitions in M and intermolecular
CT transitions occur. To account for the latter, a range-separation
parameter o suitable for intermolecular CT must be used, as
opposed to o values commonly used for intramolecular transi-
tions. The optimum o value for the two cases is sufficiently
different that TD-DFT with a single common o parameter falls
short of giving an accurate representation of the full spectrum.
In general, for noncovalent complexes in which intermolecular
CT plays a role, it could be possible to combine information
for such different types of transitions with differently para-
meterized TD-DFT methods. However, we have shown that
coupled cluster methods allows one to handle these different
transitions with similar accuracy.
Using the results of our computed toluene–O2 CT spectrum,
we estimate that the equilibrium constant for the formation of
the ground state toluene–O2 complex is B0.1 M1.
Computational methods
MD simulations were performed in Tinker 870 using the AMOEBA
force field64 and our own parametrization of molecular oxygen (see
ESI†). Initial structures were constructed using Packmol.69 Details
of the MD simulations are given in the ESI.† All quantum
chemistry computations were performed in Gaussian 16,84 except
the two-photon computations, which were done in Dalton.85 One-
photon TD-DFT computations were performed at the oB97X-D46/
6-31G(d)86 or oB97X-D/aug-pcseg-159 levels of theory with the latter
basis set taken from the Basis-Set Exchange Library.87 Two-photon
computations were performed at the CAM-B3LYP/aug-cc-pVDZ
level of theory. Coupled cluster computations were performed at
the EOM-CCSD42/aug-cc-pVDZ88 level of theory.
Conflicts of interest
The authors declare no competing financial interests.
Acknowledgements
This work was supported by the Independent Research Fund of
Denmark. The numerical results presented were obtained at
Phys. Chem. Chem. Phys., 2021, 23, 15038–15048 | 15045

PCCP
the Centre for Scientific Computing, Aarhus. The authors thank
Mikkel Bregnhøj for helpful comments and Pier Paolo Poier for
assistance with the Tinker program.
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