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Photobiological Sciences
Cite this: Photochem. Photobiol. Sci., 2011, 10, 867

www.rsc.org/pps PERSPECTIVE
Using the computer to understand the chemistry of conical intersections†
Igor Schapiro,a Federico Melaccio,a,b Elena N. Larichevaa and Massimo Olivucci*a,b
Received 27th September 2010, Accepted 11th November 2010
DOI: 10.1039/c0pp00290a

The application of computational chemistry in resolving photochemical and photobiological problems

depends on theoretical models and calculation strategies that allow an understanding of how and when
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the energy contained in a photon can be used or dissipated by a molecule. Progress in this arena has
been the result of a scientific journey that can be traced from the 1960s and 1970s with the development
of the concept of the “photochemical funnel”, and again from the 1980s and 1990s with the
development and application of ab initio multiconfigurational quantum chemistry. Mainly following the
viewpoint and contributions of the corresponding author (together with others), here we show that both
the early and the ongoing research points to a central role of conical intersections in the molecular-level
control of the selectivity and efficiency of photochemical reactions and internal conversion processes.

Introduction plemented them in computer programs that can be used to

It is conceivable that when Giacomo Ciamician and Emanuele
Paternò started to describe the effects of sunlight on organic
compounds, the need to understand why light irradiation led to
products distinct from those obtained with heat rapidly emerged.
In fact, during a famous lecture delivered in 1912 at the VIII
International Congress of Applied Chemistry in New York,1
Ciamician claimed:
“In ordinary . . . chemistry the reactions take place in some defi-
nite way, but the photochemical reactions often furnish surprises . . . ”
Nowadays we know that when an equilibrated ground state
chromophore is promoted to an electronically excited state by light
absorption, nuclear motion is triggered. The initially populated
Franck–Condon (FC) active mode may then couple to the other
available molecular modes2,3 leading to large changes in the
original molecular and electronic structures. This complex process
ultimately determines the fate of the absorbed light energy which
can either be released (via internal conversion/luminescence) or
exploited to drive a change in bonding (i.e. a photochemical
reaction). Quantum chemists (a specialized group of theoretical
chemists) view such events in terms of the evolution of the
chromophore’s nuclear coordinates along different and inter-
connected 3N - 6 dimensional potential energy surfaces, where
N is the number of atoms. Accordingly they have formulated
computationally effective electronic structure theories and im-
a
Chemistry Department, Bowling Green State University, Bowling Green,
OH, 43403, USA. E-mail: molivuc@bgsu.edu; Fax: +1 419 3729809; Tel: +1
419 3727606
b
Dipartimento di Chimica, Università di Siena, Siena, I-53100, Italy. E-mail:
olivucci@unisi.it; Fax: +39 0577 234278; Tel: +39 0577 234274
† Presented at the meeting “Ciamician–Paternò heritage. Photosciences: a
look into the future”, Ferrara, Italy, July 16–17, 2010.
compute the potential energy and its derivatives with respect to
the nuclear coordinates. Such programs constitute the instruments
of computational chemists.
A computational chemist, rather than going into a laboratory,
sits down at the terminal of a modern computer (in fact,
he/she often uses a laptop to get a web connection to one or
more powerful computers located anywhere in the world) and
uses suitable quantum chemistry software to build mathematical
models of individual molecules, groups of molecules or entire
molecular populations. Then the chemist checks whether the
model reproduces known properties of the system, and, if so,
explores the model in order to uncover information not presently
known. In this way the resolution of a chemical problem is
conducted in a virtual (in silico) reality, which nevertheless follows
the laws of physics, both classical and quantum, of real molecules.
This method of working falls perfectly in line with the conjecture
of the American chemist, Robert S. Mulliken who stated during
his 1966 Nobel Lecture:4
“In conclusion, I would like to emphasize strongly my belief that
the era of computing chemists, when hundreds if not thousands of
chemists will go to the computing machine instead of the laboratory
for increasingly many facets of chemical information, is already at
hand . . . ”
Indeed, there are technological problems that require the design
of molecules capable of responding to light in specific ways. In
the area of photoprotection, for example, molecules are required
to remain structurally unchanged while efficiently degrading the
excess electronic energy by internal conversion. Computational
chemistry is able to assist the resolution of this type of problem in a
number of ways. In the first place it can be employed to study which
mechanisms underlie the utilization or dispersion of the electronic
energy, thereby making rational design possible. In the second

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place it can be employed to verify whether a designed molecule
will respond to light in a desired way, without first synthesizing it
in the laboratory.
At this juncture we should recognize that, as in other chemical
arenas, the design of photoresponsive materials has been accom-
plished already in the evolution of biological systems. Indeed, we
are aware of biomolecules that are specialized in using the energy
of light to bring about alterations in their structure. This happens
with a yield of 67% in the visual receptor rhodopsin.5 On the
other hand, there are proteins that have become specialized in
energy removal, an example being the fluorescent protein of the
medusa Aequorea victoria, which manages to convert 80% of the
energy of ultraviolet radiation into green fluorescence.6 Therefore,
a second direction towards new materials is represented by the
computational study of the mechanisms for the utilization or
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structures) where the decay probability from an upper (excited
state) to a lower (e.g. ground state) surface is largest. These
critical structures are termed “photochemical funnels”,9–11 and
their existence is required to explain the events occurring after the
deactivation of an excited state. At a funnel, a structure evolving
on an excited state potential energy surface will hop to a lower
surface (associated either with a different excited state or with the
ground state) on a time-scale shorter than the typical radiative
decay times (ns). Such a hop either initiates the formation of a
transient/photoproduct or the relaxation to the original reactant.
If the upper and lower potential energy surfaces have the same spin
multiplicity, then the funnel corresponds to a conical intersection
(CI). If they have different spin multiplicity the funnel corresponds
to a singlet–triplet crossing, a doublet–quartet crossing, etc.
These types of funnels would mediate intersystem crossing rather

dispersion of light energy adopted by biological photoreceptors
and the search for simple synthetic compounds that can mimic
these processes.7,8 This brings back to Ciamician, who was
convinced that, to learn how a plant works at the molecular level,
it was necessary to successfully reproduce these highly efficient
processes in the lab.1
In the following, we review the theoretical models and tools
required to investigate the evolution of an electronically excited
chromophore or molecular system using modern computers
and distributed software. Mainly following the viewpoint and
contributions of the corresponding author and coworkers, we also
give a perspective of the emergence and future developments of
the field of computational photochemistry.
Photochemical funnels
To connect the potential energy surfaces driving the relaxation of
a chromophore one has to locate the points (i.e. the molecular
than internal conversion. For instance, the photophysics and
photochemistry of triplet states can, in principle, be understood
by locating singlet-triplet crossings. Below we will focus on funnels
corresponding to CIs.
Photochemical reaction paths
Photochemical reaction paths12–15 are central for the computa-
tional investigation of photoinduced processes. These are com-
pound minimum energy paths (MEPs) connecting the FC point
on the potential energy surface of the light-absorbing state to
one or more photoproduct minima on the ground state surface.
A basic photochemical reaction path (Fig. 1) involves an excited
state MEP16 connecting the FC point to two (or more) ground state
MEPs through a CI or real crossings between states of different
spin-multiplicity. In general, these crossing points connect the
excited state MEP to one describing the relaxation of the system
back to the initial reactant (an aborted photochemical reaction).

Fig. 1 The photochemical reaction path. Left: Schematic representation of the photochemical reaction path (full lines) for an ultrafast photochemical
reaction (formed by three barrierless excited state and ground state MEPs). The decay is controlled by a conical intersection (CI). The thinner full line
represents a thermal path controlled by the transition state (TS). Schematic reactive and non-reactive photochemical (i.e. non-adiabatic) trajectories are
also reported. These can be computed in terms of semi-classical trajectories (see below). Right: The same photochemical reaction path represented in a
two-dimensional diagram.

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They also connect the excited state to a different ground state MEP
which describes the relaxation of the system to the photoproduct
in a successful photochemical reaction. Notice that the aborted
branches of photochemical reaction paths describe a far-from-
equilibrium internal conversion, distinct from the traditional
process17 controlled by FC factors in the weak coupling regime
(e.g. far from a surface crossing).
The difference between a transition state (TS), i.e. the critical
structure mediating a thermal process, and a CI, a critical structure
mediating a photoinduced process is illustrated in Fig. 2. These
differ in both the local shape of the potential energy surface and
chemical significance. A TS is a stationary point located on a
potential energy surface while a CI is a singularity (i.e. the first
derivative of the potential energy is not a smooth function of the
nuclear coordinates) on both the upper and lower potential energy
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surfaces. The type of bond-breaking/bond-forming process me-

diated by a TS is described by a single molecular mode called the
transition vector. In contrast, the reactivity of a CI is described by
two molecular modes called branching plane (X1 and X2 )18 or g–h
plane (g and h)19 vectors.
Fig. 2 Critical potential energy surface structures in chemistry. Left: A
transition state. Right: A conical intersection.
Fig. 3 The mechanism of prefulvene production. Top: The photochem-
istry of benzene at 254 nm. Bottom: Geometrical and electronic structure
of the “benzvalene” conical intersection.
Recently, it has been reported21 that this photochemical process
may even involve the population of a triplet state via an ultrafast
S1 /T1 intersystem crossing and a decay through a triplet T1 /T0
rather than S1 /S0 CI. In fact evidence has been provided for the
competitive production of T0 and S0 prefulvene.21 The structure of
the T1 /T0 intersection may well be similar and nearly degenerate
to the one given in Fig. 3 but featuring an allyl radical with parallel
spin.
In Fig. 4 (left) we show the branching plane modes for the same
CI. As we explain below, and consistently with the diagram of
Fig. 2, these are the only two molecular modes capable of lifting
the degeneracy. These modes indicate the possible photochemical
processes mediated by the CI. The gradient difference vector (X1 )
clearly points to an evolution towards prefulvene where the C1–
C3 bond gets fully formed. Clearly, the opposite (-X1 ) direction
describes the reconstitution of the original benzene molecule. The
derivative coupling vector (X2 ) describes a symmetry breaking
mode leading to two Kekulé benzenes. Of course, these are

CIs provide a structurally well-defined connection between

different electronic states of the reacting species. An example of
a CI mediating a photoinduced rearrangement of a basic organic
chromophore (benzene) is given in Fig. 3.20 Upon 254 nm irra-
diation benzene produces small quantities of benzvalene (which
rearranges to fulvene) which has been proposed to be produced
via ring closure of the bicyclic diradical intermediate prefulvene.
The geometrical and electronic structure of the minimum energy
CI computed for benzene is seen in Fig. 3 bottom. The structure is
characterized by a (CH)3 moiety bearing three weakly interacting
singly occupied p-orbitals localized in the three corresponding
CH units. A fourth electron is delocalized on the SOMO orbital
of the C4–C5–C6 allyl moiety and is substantially isolated. The
remaining two electrons of the benzene p-system are on the
HOMO of the same allyl moiety. It is apparent that the CI displays
partially broken and partially formed s and p bonds. In particular
the 2 Å C1–C3 bond length is that of a half-broken s bond that can Fig. 4 Left: The branching plane vectors of the “benzvalene” conical
be seen as the precursor of the transannular bond of the prefulvene intersection. The expressions of the gradient difference (X1 ) and derivative
diradical. In conclusion, the geometry and the electronic structure coupling (X2 ) vectors are also given. Right: The branching plane diagram
of the CI correlate with the expected primary photoproduct. for the S1 /S0 CI of benzene.

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Fig. 5 Schematic two-dimensional representation of the intersection space. Left: A pictorial representation of the intersection space between two energy
surfaces (see text). The CIMEP , MECI and CITraj refer to the intersection space points located via excited state MEP calculation, conical intersection
optimization (the MECI), and trajectory computation respectively. Right: Shape of the photochemical reaction path and conical intersection region for
paths leading to peaked (top) and sloped (bottom) CIs.

electronically and geometrically unstable situations and are pre-
dicted to relax back to benzene. The result of the CI analysis is
summarized in a branching plane diagram (see Fig. 4 right).
The CI above has been obtained by computing the so called
minimum energy conical intersection (MECI). MECIs are often
assumed to correspond to photochemical funnels and, in principle,
they should be close to the point intercepted by the excited state
branch of a photochemical reaction path. However, as we will
now explain, this is only an approximation. Any CI structure is
an element of a 3N - 8 dimensional subspace (the intersection
space) of the configuration space which is formed by an infinite
collection of CIs.19,22 The intersection space is locally orthogonal
to the branching plane defined above. As schematically shown
in Fig. 5, this appears as a curve of crossing points (a seam)
when the intersecting potential energy surfaces are plotted along
a coordinate plane defined by one branching plane vector and by
one of the 3N - 8 molecular modes belonging to the intersection
space. The decay to the lower potential energy surface may occur
from any point of the intersection space. Thus, in principle the
description of the photochemical funnel of a specific reaction
requires the definition of the most chemically significant CI point
belonging to the intersection space of the reacting system. One
possibility is to assume that the excited state reactant is funnelled
to the ground state through the MECI (see Fig. 5).
As we will also discuss later, methods for locating MECI
points23–27 have been reported and are available in computer pro-
gram packages such as Gaussian,28 Molcas,29 Gamess,30 Molpro,31
Columbus32 and Firefly.33 MECIs do not necessarily correspond
to the point reached by a MEP starting at the FC point. This
means that they may not be part of the photochemical reaction
path even if they are computationally convenient. For this reason,
when possible, more meaningful CI points are defined as the first
point of degeneracy intercepted by an excited state MEP (CIMEP
in Fig. 5). This point may differ significantly from the MECI,
especially in those cases where the MEP is not orthogonal to the
intersection space.
“Photochemical” trajectories
Photochemical reaction path computations provide valuable infor-
mation on the spectroscopy (excitation energies), energy (reaction
barriers and excess vibrational energy) and mechanisms of a
photochemical reaction.15 On the other hand, this information is
only valid under the assumption that the centre of the excited state
population (e.g. a laser-generated vibrational wavepacket) would,
on average, follow a path close to the MEP. This is considered
to be a fair approximation in cases where the potential energy
valleys are deep. However, photochemical reaction paths do not
provide information on the time scale of ultrafast photochemical
or internal conversion processes15 that are characterized by a
very small excited state reaction barrier (or no barrier at all)
to control the reaction kinetics. They may also fail to provide
mechanistic information when the potential energy valleys are
flat. In these cases the mechanism and dynamics of the process
can be investigated by computing excited state classical34 or
semi-classical35–39 trajectories (see two schematic photochemical
trajectories in Fig. 1; photochemical stands for “non-adiabatic”.
This means that the trajectory can hop from the upper to the

870 | Photochem. Photobiol. Sci., 2011, 10, 867–886 This journal is © The Royal Society of Chemistry and Owner Societies 2011
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lower potential energy surface). Trajectories are computationally

demanding but they have been shown to provide predictions and
rationalizations of observed time scales even for chromophores
in solution or embedded in a protein environment (see below).
Indeed, a single classical trajectory released from the FC point
with no initial velocities (called FC-trajectory) provides a better
representation of the average motion of the centre of the excited
state population and, for this reason, it is a tool superior to MEP
computations. Moreover, it is a better tool when the upper and
lower state potential energy valleys are shallow and the motion
of the centre of the vibrational wavepacket deviates significantly
from the excited state branch of the photochemical reaction path.
In those cases, a FC-trajectory represents a better way to locate the
chemically relevant CI point along the intersection space (CITraj in
Fig. 5).
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The comparison between the excited state branch of a pho-

tochemical reaction path and a classical trajectory for a photoi-
somerization reaction occurring in methanol solution is given in
Fig. 6 for an indanylidene pyrroline switch (see below for the
method employed for the calculation of the potential energy in
large systems including biopolymers and solvent cavities).8 The
general shape of the trajectory and of the excited state MEP is
similar for this sub-picosecond reaction. In this case, as well as for
the cases discussed in the next section, there are little qualitative
differences between the path, the trajectory and the structure of
the corresponding intercepted CIs (see details in ref. 8). Therefore
the description of the excited state evolution provided by a MEP
or FC-trajectory is equivalent for such a case. However, in general,
one may expect larger deviations when the excited state lifetime
increases or for cases of flat excited state energy surfaces.
A number of groups,41–54 including ours,44 have reported non-
adiabatic semi-classical trajectories computed using suitable ab
initio quantum chemical methods and simple surface-hopping
protocols.56,57 This type of trajectory provides a description of
the entire photoinduced molecular motion (within a certain time
scale that is usually shorter than 1 picosecond) and simulates
Fig. 6 Top: S1 energy profile (diamonds) along the S1 MEP (com-
the hop from an upper to a lower potential energy surface that
puted in terms of the intrinsic reaction coordinate, IRC)40 for the
usually occurs in the vicinity of one of the intersection space
Z→E photoisomerization of the indanylidene pyrroline switch Z-1. It
points. It also provides a description of the evolution occurring is shown that the S0 -Z-1 equilibrium structure, the transient S1 -Z-1
after the hop and leading towards a photoproduct or towards the excited state structure and the CI-Z-1 are connected by a barrierless
reactant. Therefore, trajectory calculations provide information reaction coordinate. The IRC value is given in a.u. (amu1/2 bohr). The
on both the excited state lifetime (already provided by classical S0 energy profile (squares) along the computed S1 coordinate is also
trajectories), and the time scale for the formation of the product. shown. Bottom: Scaled-CASSCF/AMBER trajectory34 (see also below)
These quantities may be compared with the measured excited state simulating the S1 isomerization of Z-1. The system is predicted to reach
lifetime and photoproduct appearance time. a CI on a 300 fs timescale. The open triangles indicate single-point
As we will describe below and in the Conclusions and per- CASPT2//CASSCF/AMBER energies demonstrating that the scaled–
spectives section, in the near future the increasing availability CASSCF energy profile is only slightly off the CASPT2 energy. The
CASSCF/AMBER value of the oscillator strength f along the trajectory
of multiprocessor facilities shall remove the main limitations
is also given (full circles) providing information on the intensity of the
associated with the use of single trajectories, giving access to
transient fluorescence signal.
the systematic computation of statistical properties including
quantum yields.
concepts were introduced in two seminal papers by Van der
Some history Lugt and Oosterhoff58 and later by Devaquet et al.59 In their
work, a minimum located on a spectroscopically forbidden singlet
As seen above, photochemical funnels provide a structurally (e.g. potential energy surface (see Fig. 7 left) was proposed to provide
describing the reaction stereochemistry) and electronically (e.g. the funnel mediating the photochemical conversion of buta-1,3-
describing the homolytic or heterolytic nature of bond breaking diene into cyclobutane. The minimum was found to be associated
events) well-defined connection between different electronic states with an avoided crossing with the ground state. Therefore, the
of the reacting species. More than forty years ago, the above authors’ conclusions seemed to be consistent with the idea that

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Fig. 7 The Van der Lugt and Oosterhoff (i.e. avoided crossing) vs. the conical intersection model. Left: Schematic representation of the Van der Lugt
and Oosterhoff avoided crossing mechanism resulting from the calculations in ref. 60. Right: The Van der Lugt and Oosterhoff path appears as a one
dimensional cross-section of a more complex potential energy surfaces which have the shape of a double cone and a conical intersection (CI) as the excited
state minimum. The computed and fully asymmetric structure of the CI59 mediating the electrocyclic ring-closure of buta-1,3-diene is also shown.

potential energy curves of electronic states of the same symmetry
(such as the 1A1 and 2A1 electronic states of a buta-1,3-diene
with C s symmetry) should obey the non-crossing rule.61 On the
other hand, at the time of the Van der Lugt and Oosterhoff
calculation, the only quantity that could be computed was the
potential energy of the relevant electronic states. The first or
second derivatives of the potential energy surface (with respect
to the nuclear coordinates) could not be calculated at that time.
Since these quantities are instrumental for the numerical methods
used to follow downhill paths along a potential energy surface and
therefore to locate local minima, the authors had to assume that
the funnel was located along a linear path connecting reactant
to product and consistent with the photochemically allowed
(disrotatory) electrocyclic ring-closure of the diene.
An excited state decay time corresponding to the avoided cross-
ing energy gap (ca. 30 kcal mol-1 ) estimated by Van der Lugt and
Oosterhoff is on the order of nanoseconds, comparable to typical
fluorescence lifetimes.62 However, the weak or absent fluorescence
observed in many chromophores63 and, most importantly, the
discovery of ultrafast photochemical reactions64,65 indicate that the
energy gap between excited and ground states is smaller than a few
kcal mol-1 . Early versions of the theory of radiationless transitions
were dominated by the application of Fermi’s golden rule17,66,67 and
seemed to provide a good description for the weak coupling cases
where the time scales for internal conversion and fluorescence
are comparable. However, such a theoretical framework cannot
explain ultrafast events.
The search for funnels that could explain the selectivity of
photochemical reactions led Zimmerman,68 Michl69 and Salem70
to independently suggest that the formation of specific products
can be explained by the presence of CIs. Unlike an avoided
crossing, a CI corresponds to an actual crossing of the potential
energy surfaces associated with two electronic states of the same
spin multiplicity. The original work on the crossing of potential
energy surfaces of the same spin multiplicity appeared in 1929
and was written by von Neumann and Wigner71 Following
contributions were given by Teller72 and Herzberg and Longuet-
Higgins.73 It was proposed that: (i) the non-crossing rule, which is
valid for diatomic systems, fails in polyatomic molecules where two
states are allowed to cross even when they have the same symmetry
and (ii) this crossing is conical rather than linear. Teller74 also
suggested that radiationless decay in the vicinity of intersection
spaces takes place within a single vibrational period.
Nowadays we know that the photochemical conversion of buta-
1,3-diene to cyclobutene is mediated by a CI (see Fig. 7 right).75,76
We also know that such a CI is fully asymmetric and that therefore
the two intersecting states belong to the same space and spin
symmetry. These results have been produced after much progress
in the development of ab initio multiconfigurational quantum
chemistry methods (see below). These methods currently allow
the computation of both potential energies and their first and
second derivatives at a level of accuracy that allows a comparison
between computed energy gaps and the energy of corresponding
spectroscopic transitions (e.g. absorption and emission maxima).
The implementation of ab initio multiconfigurational quantum
chemical methods in computer programs towards the end of
the 1980s was fundamental for the consolidation of the idea
that CIs were a diffuse form of photochemical funnels. With
such techniques available, it became possible for the chemist to
efficiently calculate more correct potential energy surfaces, which

872 | Photochem. Photobiol. Sci., 2011, 10, 867–886 This journal is © The Royal Society of Chemistry and Owner Societies 2011

allowed the earlier limitations on the study of photochemical
reactions to be surmounted. The principal tool at this stage of
research was the MCSCF (“Multi Configurational Self Consistent
Field”) method one version of which was developed in Great
Britain in the lab of Michael Robb.
The MCSCF method was formulated in a 1955 article
by Löwdin;77 at that time it was referred to as “Extended Hartree–
Fock”. In 1976, Ruedenberg and Sundberg78 published a paper
which outlined a methodology called “Fully Optimized Reaction
Space” which is very close to the main method used today for
photochemical studies. Nevertheless, because of the mathematical
methods of that time, the calculations were too complex and costly
to be of use to the chemist. Clearly there was a need of further
advances in order to routinely perform significant calculations. In
this article it is not possible to indicate all the contributions to the
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writing of an efficient computer program. Often these represent
only partial solutions of the computational problems that must
eventually describe the structure of molecules in full complexity.
An early application of the MCSCF method for the description
of the excited state potential energy surface of reactive entities has
been reported for the formyloxyl radical.79 In this contribution
surface crossings were also located. However, the first application
of the MCSCF method to organic photochemistry, or better its
close relative CASSCF (“Complete Active Space Self Consistent
Field”) was carried out in 1990 in the work of an Italian-British
group formed by Robb in London and Bernardi in Bologna.80 At
that time they were seeking a demonstration of the stereoselectivity
rules observed for pericyclic reactions. Their interest was focused
on the case of supra-supra cycloaddition leading to the production
of cyclobutane: a thermally forbidden process. Using a fast
computer and the ab initio CASSCF methodology, they were able
to map the reaction path starting from ethene. The calculations
were performed by one of the authors of the present paper during
a visit to Robb’s lab at King’s College in London. A CI in which
four carbon atoms sit at the vertices of a rhomboidal ring was
found in a deep minimum on the energy map of the excited state.
For these calculations it was necessary to use one of the fastest
computers of the time, namely, the CRAY Y-MP.
The ab initio multiconfigurational quantum chemical methods
are currently the only methods widely applied in photochemical
studies. This is due to the flexibility and unbiased nature of
the associated wavefunctions. Techniques such as time-dependent
density functional theory (TD-DFT)81 have also been used82
and successfully applied to the investigation of a number of
spectroscopic problems in systems as large as porphyrins83,84
and phthalocyanins.85 However, the present common TD-DFT
functionals are accurate only for excited states dominated by
single excitations, failing to correctly describe regions near conical
intersection.86 Indeed, conical intersections involving a closed-
shell singlet initial state cannot exist in TD-DFT (the interaction
matrix elements connecting the initial state and response states
are excluded from the formulation). This gives rise to surface
intersections where only one molecular displacement breaks the
degeneracy.86 Until these problems are solved by the development
of new functionals that can deal with the multiconfigurational
character of the electronic structure, this method has limited
applications in the study of photochemical processes. Therefore all
the studies reviewed in the present contribution will focus on the
CASSCF and complete active space second order perturbation
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theory (e.g. ab initio CASPT2)87 methodologies (see below). In
fact, at the CASSCF level, static electron correlation is taken
into account, allowing for the treatment of situations involving
partially broken bonds and the development of diradical character.
However, in order to reproduce the spectroscopic parameters (e.g.
absorption and fluorescence maxima), the remaining dynamic
electron correlation effects need to be included. This can be
achieved, for instance, using the CASPT2 method mentioned
above. The CASPT2//CASSCF protocol, where one carries
out the potential energy surface mapping at the CASSCF level
and then corrects the energies of chemically meaningful points
(e.g. energy minima and CIs) by running single point CASPT2
calculations has been extensively used in the past and has been
shown to reproduce experimental observations within a few kcal
mol-1 .9,14
As illustrated in Fig. 7 (right), the computation of the excited
state MEP at the CASSCF level helped to clarify the rela-
tionship between the avoided crossing found by Van der Lugt
and Oosterhoff and the computed buta-1,3-diene/cyclobutene
CI. Constraining the reaction path to follow a linear coordinate is
equivalent to slicing the potential energy surfaces along a specific
one-dimensional cross-section where the CI degeneracy appears
to be lifted and is replaced by an avoided crossing. When this
constraint is released, and the potential energy is minimized along
all possible 3N - 6 molecular modes, it is found that the local
minimum corresponds to a real crossing (i.e. a MECI).
The “chemistry” of conical intersections
Attempts to predict and computationally locate conical intersec-
tions in model organic chromophores were reported by Michl and
Bonačić-Koutecký in the 1980s.88–92 The idea that conical intersec-
tions could provide efficient photochemical funnels and that could
even play a role in photobiology was reported in a book.93 During
the following years other groups employed emerging quantum
chemical technology to investigate the mechanisms of photochem-
ical reactions. In the period from 1990 to 2000, Bernardi, Robb,
Olivucci and coworkers studied 25 different compounds involved
in 16 different types of photochemical reactions.22 Other CIs were
reported by Ruedenberg,94–96 Martı́nez,48,52,97 Domcke,98–103 Koppel
and Cederbaum,104–106 Yarkony107–110 and Klessinger111–114 for dif-
ferent molecules. These CIs were usually located as MECI points.
Accordingly, during these studies the availability of methods to
locate (optimize) minimum energy points of the seam of crossing
between two potential energy surfaces was critical. One first
version of this methodology,115 based on the computation of the
derivative coupling and branching plane vectors, was based on an
extension of a method developed by Morokuma and coworkers.24
A more effective methodology was reported by Robb, Schlegel
and coworkers.23 Other methods were developed independently by
Yarkony and coworkers,25 who developed methods for locating
multiple state intersections.116 Martinez and coworkers have re-
ported and tested a method for locating MECI that does not need
the computation of the non-adiabatic coupling vector.117 Robb has
also reported a MECI optimization method based on analytical
Hessians.27 Recently Morokuma and coworkers have reported an
effective branching plane updating method118 that does not need
the computation of the non-adiabatic coupling vector, yet provides
information on the branching plane orientation.
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Fig. 8 Three types of chemical processes mediated by CIs in different hydrocarbons.
The analysis of the corresponding pool of CI geometries
and electronic structures demonstrated that all basic chemical
events (bond breaking, bond making and the transfer of bonds
between centres) were represented. This mechanistic concept and
the supporting results were highlighted in 1995119 and 1996.9,10
Examples are given in Fig. 8 for the CIs mediating the photochem-
istry of benzene,20 cyclohexa-1,2-diene60,120 and norbornene.121 As
discussed above, the benzene CI mediates a covalent bond-making
process. The cyclohexa-1,3-diene CI is mediating a covalent
bond breaking process allowing the formation of a diradical
intermediate and a concerted ring opening. The norbornene CI
mediates a rearrangement (a concerted [1,3] sigmatropic shift)
displaying both bond-breaking and bond-making processes. The
same examples also demonstrate that similar chromophores (un-
saturated hydrocarbons) react via structurally and electronically
similar CIs. All CIs display four weakly interacting electrons.
Covalent chemistry
The CI mediating the ring opening of cyclohexa-1,3-diene is an
example of a funnel leading to the simultaneous formation of two
photoproducts (the adjective “simultaneous” has to be understood
in terms of reaction mechanism and, more loosely, photoproduct
formation time).122 However, the products form with different
quantum yields. As shown in Fig. 9 top, its photolysis leads
to the formation of hexa-1,3,5-triene and of a lower yield of
bicyclo[3.1.0]hexa-2-ene. The simultaneous formation of these
products can be explained on the basis of the electronic and
geometrical structure of the CI (see Fig. 9 bottom). The CI
suggests that the photoproducts can be formed by re-coupling
the electrons of the triangular arrangement formed by carbons
C1–C2 and C6 in different ways. In particular, the re-coupling of
the unpaired electrons on C1 and C2 and, consequently, of the
electron on C6 with the remaining unpaired electron located on
a central allyl moiety yield an unstable conformer of hexa-1,3,5-
triene. On the other hand, the re-coupling of the unpaired electron
on C2 with the electron on C6 yields a diradical species precursor
of the observed bicyclo[3.1.0]hexa-2-ene. Notice that, the third,
possible re-coupling mode, i.e. the re-coupling of the electrons on
C1 and C6 yield the original reactant cyclohexa-1,3-diene. This
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last process can be interpreted as an internal conversion or as an
aborted photochemical reaction.
In the bottom of Fig. 9 we display the X1 and X2 vectors for
the cyclohexa-1,3-diene CI. It is apparent that the two molecular
modes are consistent with the processes described above and once
again demonstrate that these vectors have, for photochemical
reactions, the same significance that the transition vector has for
thermal reactions. Displacement along X1 leads to the formation
of hexa-1,3,5-triene in a s-cis,Z,s-cis conformation. -X1 is instead
describing the reconstitution of the reactant. In contrast, X2
describes the formation of a diradical intermediate with the
unpaired electrons located on carbon C1 and on a central allyl
fragment. Finally, the -X2 displacement is pointing to an unstable
and different diradical structure with the unpaired electrons
localized on C1 and C6. The branching diagram of Fig. 9 (bottom)
summarizes the result of the analysis of the CI structure and
branching plane vectors.
The ring opening considered above has shown how, in principle,
more than one photoproduct can be generated starting from the
same CI. However, the decay to the lower potential energy surface
may occur from any point of the 3N - 8 dimensional intersection
space (any CI structure is an element of an intersection space
formed by an infinite collection of CIs).18,19,22 Therefore, there
is another way in which irradiation of a given chromophore
can result in the production of more than one product. In
fact, CI optimizations and branching plane analysis reveal the
widespread existence of chemically different MECIs belonging
to the same intersection seam.123 By “chemically different” we
mean that each MECI displays a different bond-breaking and/or
bond-forming process. As a consequence, different photoproducts
can be formed starting from the same reactant system whenever
the excited state evolution allows the reactant to achieve these
different photochemical funnels. In Fig. 10 we report 4 different
MECIs that belongs to the intersection space of the polyene deca-
1,3,5,7,9-pentaene. Three CIs lead to different bicyclic systems
via production of different 1,3-diradical intermediates. One CI
would, in principle, lead to a cyclopropyl diradical intermediate
but can also mediate the Z/E isomerization of the polyene
double bond incorporated in the ring moiety. This last CI is the
lowest in energy and, most likely,60 the one that dominates the
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Fig. 9 The CI mediating the photochemistry of cyclohexa-1,3-diene.

Fig. 10 Deca-1,3,5,7,9-pentaene CIs mediating different chemical reactions and belonging to the same intersection space.

polyene decay in hydrocarbon solution (i.e. in an environment Charge transfer chemistry

similar to the gas-phase model of the calculation). However, the
structure of the intersection space indicates that a new form
of (photochemical) reaction selectivity is possible whenever the
polyene is incorporated in a molecular cavity or is part of a
larger molecular or supramolecular structure that stabilizes the
higher energy intersections with respect to the one leading to Z/E
isomerization.
Conical intersections in radical cations were found by Lorquet
and coworkers124 as well as by Köppel, Domcke, Cederbaum and
coworkers100,105,110,125–129 in the 1970s and early 1980s. More recently,
the presence of CIs on the potential energy surfaces of radical
cations has been detected and investigated at the CASSCF level
by Bally and co-workers.130,131 Radical cations also offer examples

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where a CI mediates charge (electron) transfer. This is associated
with a change in electronic structure involving the transfer of an
electron between two atomic centres and not exclusively a change
in spin-pairing as seen above for covalent chemistry. Recently, it
was documented132 such an event while studying the mechanism
of non-radiative decay in an open-shell mixed-valence compound,
consisting of two identical charge-bearing units (M) connected by
a molecular bridge (B). We have shown133 that the radiationless
deactivation of the initially planar N,N,N¢,N¢-tetramethyl-p-
phenylenediamine radical cation134,135 (Wurster’s blue) is mediated
by a D1 /D0 CI (see structure in Fig. 11) characterized by
the intersection of electronic states with very different electron
distributions. In fact, the excited state evolution is characterized
by the displacement of the unpaired electron from an initially
delocalized position, on two C NMe2 bonds, to the phenyl bridge
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and finally to a single –NMe2 group. This last event is driven by
a coupled bond stretch and twisting deformation of the –NMe2
group carrying the radical centre. The CI is reached when such
group is fully twisted.
Fig. 11 Wurster’s blue D1 /D0 CI. Top: Geometrical parameters (Å)
of the gas-phase D1 /D0 CI computed at the CASSCF/6-31G* level
of theory and an active space comprising the full p-system. Bottom:
Molecular orbitals hosting the unpaired electron in the D1 and D0 state.
The resonance formulas illustrating the electronic structures of the CI in
the corresponding D1 and D0 states are also given.
Upon decay the electronic structure changes by moving a single
electron from a doubly occupied p-orbital of the phenyl ring into
the singly occupied p-orbital of the twisted NMe2 group (orbital D1
in Fig. 11). During the D0 relaxation (i.e. after decay at a D1 /D0
CI) the unpaired electron moves back to the bridge and, after
planarization of the twisted NMe2 group, to the original D0 charge
distribution. The NMe2 twisting required to reach the conical
intersection in Wurster’s blue points to a twisted intramolecular
charge transfer phenomenon136,137 associated with the D1 to D0
decay.
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CI mediating intramolecular electron (charge) transfer have also
been documented in biological relevant closed-shell chromophores
such as the penta-3,5-dieniminium cation of Fig. 12. The CI
mediates the Z/E isomerization of the central double bond of
the chromophore providing a model for the 11-cis to all-trans
photoisomerization13,138,139 of the retinal chromophore of visual
pigments (see Fig. 12 top and next section). Upon decay at a CI
where the central, isomerizing, double bond is ca. 90◦ twisted, the
molecule relaxes along two possible paths characterized by a S0
electron distribution that initially has a diradical rather than closed
shell character. The excited state path and the two relaxation paths
have been documented by computing the corresponding three
MEP (computed in terms of IRCs). These MEPs constitute an
example of a fully documented photochemical reaction path (see
above). Notice that, as for Wurster’s blue, the CI is characterized
by the crossing between two states with a different location of a
single electron. In the case of Wurster’s blue the electron is located
in a NMe2 unit in D1 and on the phenyl ring in D0 . In the case of
the penta-3,5-dieniminium cation, the moving electron is mainly
located on the C N containing part of the conjugated chain in
S1 while it is located on the opposite side (yielding an unstable
diradicaloid structure) in S0 . Notice that in both cases the CIs
have one fully twisted double bond.
Dynamics at conical intersections
While the above discussion focuses on the “static” mapping
of the relevant potential energy surfaces and the location of
chemically meaningful conical intersection points, the excited
decay process occurring at a CI and, consequently, the fate of
the excited state population after decay are determined by non-
adiabatic effects. This fact is of great importance not only for the
correct simulation of the observed selectivity of photochemical
reactions, but also for its control (for example, see ref. 140).
While, as mentioned below, the computation of semi-classical
photochemical trajectories currently represents a practical way to
address this problem, it is important to mention that Domcke,101,102
Koppel,141 Cederbaum,105 Martinez48 and coworkers provided the
first rigorous demonstrations of ultrafast dynamics at conical
intersections. This was at a time when the prevailing picture of
radiationless decay implied that a large number of vibrational de-
grees of freedom are a necessity for efficient deactivation.17,67,142–144
The demonstration, by quantum dynamics calculations, that
few vibrational degrees of freedom are sufficient for irreversible
radiationless decay at conical intersections led to a fundamental
change of paradigms in radiationless decay theory. This change
is not less important than the above-mentioned computational
demonstration that low-lying CIs are ubiquitous and common
features of the excited states of sizable organic and biological (see
also below) molecules.
Conical intersections in proteins
While ab initio multiconfigurational quantum chemical methods
such as CASSCF and CASPT2 have been successfully applied
to sizable organic molecules, their computational cost makes
application to large and/or complex molecular systems im-
possible. These systems include chromophores in solution and
chromophores embedded in a protein environment such as the

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Fig. 12 The computed photochemical reaction path for a minimal (penta-3,5-dieniminium) model of the chromophore of the visual pigment rhodopsin
(the protonated Schiff base of 11-cis retinal. See top).
visual photoreceptor mentioned above. The increasingly popular
methodology which offers a solution to this problem is the
hybrid quantum mechanical/molecular mechanical (QM/MM)
method.145 The underlying idea is to combine the accuracy of
quantum mechanical (QM) methods and the low computational
cost of molecular mechanics (MM) methods. The history of hybrid
methods starts more than thirty years ago with Warshel’s work on
lysozyme, where a MM method was coupled to semi-empirical QM
calculations.146 This type of calculation was soon after applied to
the study of visual pigments147 and therefore to photobiology.
In a QM/MM setup, the part of the system (QM subsystem)
which is responsible for the reactivity, spectroscopy, photophysics
and photochemistry, is described by a suitable quantum chemical
method. The remaining part (MM subsystem), such as a box of
solvent molecules or the protein hosting the QM subsystem is
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described in a computationally inexpensive way at the molecular
mechanics level (i.e. using parametrized classical force fields). The
total (relative) potential energy of the system can be described by
the additive formula:145 E Total = E QM + E MM + E QM/MM . While the
first two terms account for the contributions coming from non-
interacting QM and MM subsystems, the third term describes
their interaction. Notice that there are different E QM and E QM/MM
terms for each electronic state while the E MM remains the same.
The general classification of QM/MM methods is based on the
formulation of the E QM/MM term and on the scheme adopted to
describe the boundary region between the QM part and the MM
part. Depending on the way in which electrostatic interactions are
treated, the QM/MM schemes can be divided into two classes:
mechanical embedding (ME) and electrostatic embedding (EE).148
In photochemical and photobiological studies we need to use an
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EE method. In these methods the QM computation is carried out
in the presence of the MM subsystem by including the description
of the electrostatic interactions between the two subsystems
in the one-electron operators of the QM Hamiltonian. The
remaining non-bonding interactions (van der Waals) and bonding
(stretching, bending and torsional) interactions are treated at
the MM level. It is usually convenient to represent the MM
atoms by atomic-centered partial point charges for the purpose of
calculating electrostatic interactions. Sets of these point charges
have been calculated and incorporated into popular MM force
fields, like CHARMM149 or AMBER.150 Some advantages of using
these MM charges are that they have been validated extensively
and have been parametrized to give accurate MM energies.
In cases where there is direct bonding between the QM and MM
subsystems, such as for a chromophore covalently linked to
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the protein (e.g. fluorescent proteins or visual pigments) the
E QM/MM term also includes bond, angle, and torsional parameters
accounting for the treatment of the frontier bonds (the bonds
that connect the QM and MM moieties). The simplest and most
popular approach to treat the frontier bond is the “link-atom”151,152
scheme, where the free valencies of the “frontier atoms” are
saturated with one or more hydrogen atoms which are included in
the quantum chemical treatment of the QM fragment.
The parts of a QM/MM model for the visual receptor rhodopsin
(Rh) are shown in Fig. 13. The positions of the frontier bond
and link-atom are highlighted. The QM subsystem (the retinal
chromophore of the rhodopsin) and the covalently linked amino
acid side-chain included in the MM subsystem are also high-
lighted. To make the optimization more effective without losing
accuracy only the QM subsystem and part of the MM subsystem
significantly interacting with it (including nearby residues or water
molecules connected to the QM subsystem via hydrogen bonds)
are incorporated in the set of nuclear coordinates allowed to
relax. The geometry of the rest of the model is kept fixed at
the observed crystal structure required for building the model
(however, in principle, this can be replaced by a structure obtained
via homology modeling).
QM/MM models of several proteins have been constructed
and investigated by different research groups including ours162
(see the references in Fig. 13 caption). In order to provide
an example of the use of these models in reactivity studies,
we now discuss the use of single classical and semi-classical
trajectories (see above) in the study of the mechanism of the low-
temperature (77 K) photochromic equilibrium in Rh.163 In general,
the calculation of a single photochemical trajectory does not
provide real statistical information because a single trajectory does
not describe the average motion of the whole reacting population.
However, they can be employed in mechanistic studies in those
cases when a trajectory released from the FC point with zero
velocities (i.e. the FC trajectory) is expected to follow/represent
the evolution of the centre of the excited state population. This
is assumed to be the case for sub-picosecond photochemical
reactions where the excited and ground state valleys do not display
a large curvature. As we will emphasize in the Conclusions and
perspectives section, the increasing availability of multiprocessor
facilities like parallel computers, clusters and computer farms
is presently paving the way for computations of statistically
meaningful trajectory ensembles.42,51,55,58 In fact, the difficulties
associated with the use of single trajectories could be overcome by
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computing statistical properties (including quantum yields) over
tens or hundreds of semi-classical trajectories.54 Semi-classical
treatments have been shown to yield values of the quantum yield
for the photoisomerization of Rh that approach the observed
one.54
As anticipated above, as an example of mechanistic application
of QM/MM classical excited state trajectory computations we
focus on the photo-induced double bond isomerization of a
retinal chromophore embedded in a protein environment. These
trajectories have been computed using a CASSCF/Amber force
field where the CASSCF level is used to treat the QM subsystem
while the Amber empirical force field for protein is used to
describe the MM subsystem. The excited state lifetimes of Rh,34
and its reactive intermediate bathorhodopsin (Batho-Rh)163 have
been estimated by computing the time necessary to reach a CI
starting from the FC point. The calculation reveals that this time
corresponds to the time required for the partial isomerization of
the corresponding retinal chromophores (the 11-cis and all-trans
isomers of the protonated Schiff base of retinal for Rh and Batho-
Rh respectively). The Rh CI has been recently detected more di-
rectly using higher resolution transient absorption spectroscopy.55
In Fig. 14, top, we report a comparison between the energy
profiles along the classical trajectories of Rh (Rh→Batho-Rh
isomerization) and Batho-Rh (Batho-Rh→Rh isomerization).
The ca. 100 fs observed lifetime of Rh has been reproduced. It
is apparent that Rh reaches an intersection space segment which
is partially explored by the classical excited state trajectory (again,
by definition a classical, adiabatic, trajectory cannot decay to the
ground state). Batho-Rh is predicted to have an extremely short
lifetime (ca. 70 fs), consistent with the distorted nature of its all-
trans chromophore. However, this intermediate also reaches an
intersection space segment. An analysis of the CI points belonging
to the two segments as well as nearly matching energies indicates
that the intercepted intersection space is the same but it is accessed
from different directions. Indeed, in a recent work we have shown
that the same intersection space is also connected to the conical
intersection reached during the photoisomerization of Iso-Rh.164
In Fig. 14, bottom, we display other Rh excited state classical
trajectories computed with different initial conditions where the
initial geometry is displaced from the FC geometry in different
ways. It is clear that the trajectories are all similar thus providing,
at least for Rh, a validation for the use of a single trajectory in
mechanistic studies.
The results above are useful to interpret the results of more
realistic semi-classical (i.e. non-adiabatic) trajectory computa-
tions. For instance in Fig. 15 we show that the semi-classical
trajectories computed for Rh and Batho-Rh, and describing the
same low-temperature photochromic interconversion studied with
the classical trajectories of Fig. 14. The trajectories reveal that not
only the decay region but also the region of the vibrationally hot
photoproducts are reached on a sub-picosecond time scale. Also,
it is apparent that while the excited state parts of these trajectories
are substantially the same as those of Fig. 14, there are, of course,
differences in the decay regions. It is evident that for Rh the
trajectory remains close to the intersection region immediately
after its decay. This does not happen for Batho-Rh where the
intersection space is immediately abandoned and the evolution on
the ground state potential energy surface begins immediately. We
believe that in the future the understanding of these differences
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Fig. 13 Top: Partial view of the CASSCF/AMBER (QM/MM) model used for simulating the spectroscopy and photochemistry of a biological
photoreceptor (e.g. the bovine rhodopsin displayed in the figure). The protein backbone and the cavity residues (the study of the photochemical step
in these systems requires sub-picosecond simulations that do not allow for important displacements of the cavity residues) are kept fixed at their
crystallographic positions. Bottom: A CASPT2/CASSCF//MM method (see text) has successfully reproduced the excitation energies of a set of protein
pigments related to bovine rhodopsin (Rh and related isomers batho-Rh and iso-Rh and mutants E113D and G123L),153 bacteriorhodopsin (bR),154
Anabaena sensory rhodopsin (ASR),155 the green fluorescent protein (GFP),156 the photoactive yellow protein (PYP),157 the tryptophan-containing
proteins parvalbumin (Parv)158 and monellin (Mone),158 luciferase,159 Dronpa160 (a mutant of a GFP-like protein named “Dronpa” after “dron”, a ninja
term for vanishing, and “pa”, which stands for photoactivation) and phytochrome.161

at the level of the single molecular vibrational modes driving the
excited state dynamics and the hop event will become of great
importance.163
Conical intersections for different photoresponsive proteins and
protein chromophores besides Rh have been located using the
CASSCF method and are currently expanding. Here we mention
the cases of the PYP photoreceptor165 and its chromophore,166
the GFP,167 the fluorescent protein asFP595168 and the firefly
bioluminescence emitter.169
Conclusions and perspectives
The correct formulation of the mechanism of a photochemical
reaction requires the computation of real crossings, like CIs
and singlet–triplet crossings, between different potential energy
surfaces. In ultrafast reactions, CIs (and singlet–triplet crossings)
are reached on the timescale of a few vibrational periods. However,
slower processes can also be mediated by these excited state
decay channels. In fact, there are cases where access to a CI is

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Fig. 14 Scaled-CASSCF/Amber classical trajectories for S1 Batho-Rh and Rh. Top: Rh→Batho-Rh (left) and Batho-Rh→Rh (right) potential energy
profiles along the corresponding S1 classical (adiabatic) FC trajectory. Bottom: Rh→Batho-Rh S1 classical (adiabatic) trajectories characterized by
different initial conditions (i.e. not starting from the FC point with zero velocities; see ref. 34 for details).

Fig. 15 Scaled-CASSCF/Amber semi-classical trajectories for S1 Batho-Rh and Rh (the scaling of the CASSCF energy is used to simulate the effect
of a CASPT2 computation; see ref. 34). The S1 and S0 energy profiles along the S1 trajectory of Rh is given on the left. The data for Batho-Rh are given
on the right. The more accurate CASPT2 energy along the computed trajectory is also given to provide evidence that the Scaled-CASSCF and CASPT2
energy profiles are similar.34

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Fig. 16 “Parallel” photochemical research in Giacomo Ciamician’s lab (from 1889 to 1921) in Bologna, Italy, and a modern computer farm. In both
cases different sets of compounds are investigated simultaneously either experimentally or in silico.
controlled by a non-negligible excited state barrier (see Fig. 5
right). In other words, the involvement of CIs in chemistry may
go considerably beyond the field of femtochemistry and comprise
processes such as photoinduced electron transfer, quenching and
internal conversion. It is evident that a growing need to locate and
calculate CIs effectively will drive further research.
Above we have clarified that MECIs are, in general, crude
representations of photochemical funnels. This is due to the
fact that CI points are elements of complex intersection spaces.
Two more effective strategies to locate meaningful photochemical
funnels have been revised. These are photochemical reaction
paths and trajectories. However, single (classical or semi-classical)
trajectories only yield an approximation of the most meaningful
CI. In contrast the chemically most meaningful CI structure and
its properties (e.g. the excited state and photoproduct appearance
times) have a statistical meaning and can only be computed
in terms of an average structure. Therefore further progress in
the field of computational photochemistry and photobiology is
associated with the development of efficient methods for the
computation of a large set (e.g. a hundred) of semi-classical
trajectories.54,170 These methods are characterized by: (i) the way
in which the initial set of geometries and velocities are generated,
(ii) the way in which the hop decision is taken for each trajectory
and (iii) the QM/MM protocol used for computing the potential
energy and its gradients.
The computations of large sets of semi-classical trajectories
associated with trajectory surface hopping is the closest to
classical dynamics and it is the simplest to implement, but it
converges slowly to the correct average value (i.e. large num-
ber of trajectories are required). The development of ab initio
multiple spawning (AIMS), multi-configuration time-dependent
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Hartree (MCTDH) and variational multiconfiguration Gaussian
wavepackets (vMCG) try to address this issue (see ref. 38 for a
discussion of these methods). AIMS solves the time-dependent
Schrödinger equation more rigorously, but as its basis functions
follow classical trajectories it suffers from poor convergence.
vMCG is harder to implement, but its basis functions do not
follow classical trajectories and it converges much faster.
For the formulation of the QM/MM protocol to be used in
photochemical and photobiological studies, one would want to
use quantitative methods such as the CASPT2 (or the more
advanced MS-CASPT2171 ) or MRCI methods.44,172 In principle,
these methods will make sure that the forces acting on the nuclear
coordinates and driving both the excited state dynamics and the
following ground state relaxation are realistic. In this way one
could avoid non-negligible errors coming from the difficulties of
parametrizing and validating semi-empirical methods, scaling the
energies and gradients of CASSCF or formulating/parametrizing
novel functionals for TD-DFT energy and gradient calculations.
However, these advanced methods need further performance
improvements (the performance of correlated functionals is
still under investigation; see, for instance, ref. 173, 174). In
particular, CASPT2 analytical gradients are not available and
both geometry optimizations and trajectory computations can
only be performed for relatively small molecular systems.175–178
Furthermore the validity of CASPT2 energies and gradients in
the strict vicinity of a CI requires a careful analysis. However, the
more reliable MRCI method has a much higher computational
cost and it is presently of limited applicability to sizable organic
systems.
The search for realistic and computationally effective QM/MM
excited state force fields is perhaps the most important technical
Photochem. Photobiol. Sci., 2011, 10, 867–886 | 881

challenge that modern computational photochemistry and pho-
tobiology have to face. The further development of such force
fields would allow the exploitation of the constantly expanding
computational facilities. In particular, facilities going from in-
house computer clusters up to extensive computer farms available
at state or federal computer centres are especially suited for the
simultaneous investigation of large families of different molecular
systems or for the simultaneous computations of statistically
meaningful sets of trajectories of a given chromophore. It is
apparent that this last target will have a significant impact in our
understanding and future engineering of the light energy exploita-
tion at the molecular level and, therefore, in the development of
new functional materials.
The use of a computer farm for the simultaneous investigation
of a chromophore or a family of related chromophores in solution
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or in a complex protein environment is reminiscent of the way in
which one of the fathers of modern photochemistry used to carry
out his research. In Fig. 16 we see how Giacomo Ciamician used
to expose entire sets of different organic compounds to sunlight
on a balcony of his laboratory in Bologna (Italy).179 In a sense,
the opportunities described above are shifting this effective way
of carrying out photochemical research to the virtual (in silico)
world and constitute an extraordinary link between the past and
the future of photochemistry. Notice that such in silico parallel
research is not only limited to exploring the photochemistry of
different compounds simultaneously. The same technology can
be used to simulate the photoinduced dynamics of a statistically
meaningful set of configurations and atomic velocities of the
same molecular system. This provides access to a more realistic
interpretation of time-resolved spectral data and to systematic
prediction of quantum yields.
Finally we like to highlight that part of the solution to the
problem of the high cost of QM computations and, in turn, to the
enlargement of the QM subsystem in QM/MM computations can
come from modern hardware and software technology. Currently
great interest and remarkable research work are directed towards
the efficient implementation of ab initio quantum chemical meth-
ods on GPUs normally used in the video games market.180–184
The implementation of multiconfigurational quantum chemical
methods into codes that can exploit the architecture of such
processors will certainly open up new alleys for excited state
computations of large molecular systems.
Acknowledgements
This work was supported by the Center for Photochemical
Sciences and the School of Arts & Sciences of Bowling Green
State University. This perspective is, partly, the result of the
exciting years spent by the corresponding author in the labora-
tories of Fernando Bernardi at the University of Bologna and
Michael A. Robb at King’s College London. Mike, now at Imperial
College London, is especially acknowledged for his great support.
Likewise, this contribution would not have been written without
the support of outstanding coworkers, to only some of whom it
is possible to give mention here. We would like to thank Paolo
Celani, Marco Garavelli, Adalgisa Sinicropi, Annapaola Migani,
Nicolas Ferré, Luis Manuel Frutos, Tadeusz Andruniów, Pedro
Coto, Fabrizio Santoro and many others.
882 | Photochem. Photobiol. Sci., 2011, 10, 867–886 This journal is © The Royal Society of Chemistry and Owner Societies 2011
View Article Online
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