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Role of Multistate Intersections in Photochemistry

Lin Shen, Binbin Xie, Ziwen Li, Lihong Liu, Ganglong Cui, and Wei-Hai Fang*

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ABSTRACT: It has been generally accepted that the intersection of potential energy surfaces can
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facilitate nonadiabatic transitions and plays a crucial role in photochemistry. Although most previous
studies have focused on the conical intersection of two electronic states, multistate intersections are
common in polyatomic molecules, and their key roles in photochemistry have been uncovered by
electronic structure calculations and nonadiabatic dynamics simulations. In this Perspective, the
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algorithms for searching two- or three-state intersections are first examined with an emphasis on the
latest development in a general algorithm for location of multistate intersections. Then, we focus on
intersystem crossing (ISC) that occurs in the region of multistate intersection, paying more attention
to how the state-specific spin−orbit coupling interaction influences nonadiabatic ISC processes.
Finally, the interweaving of nonadiabatic dynamics simulation and electronic structure calculation has
been recognized as a correct way to ascertain the vital roles of multistate intersections in
photochemical reactions.

T he Born−Oppenheimer (BO) approximation, also known

as adiabatic approximation, assumes that the motion of
atomic nuclei and electrons in a molecule can be separated and
allows the wave function of a molecule to be broken into its
electronic and nuclear components.1 Based on the BO
approximation, the basic concept of adiabatic electronic state
or potential energy surface has been established in chemistry,
physics, and other related fields. However, the BO approx-
imation breaks down frequently, because of the strong
coupling between electronic and nuclear motion.2,3 For
example, the energy gaps of excited electronic states are
usually small for polyatomic molecules and radiationless
transition from one adiabatic excited state to another, i.e.,
nonadiabatic transition, takes place very easily. Photochemical
reactions and photobiological processes are generally initiated
from one excited adiabatic electronic state that is usually
populated by ultraviolet (UV) or visible light irradiation.4 The
excess energy from electronic excitation can be converted to
the vibrational energy, which is often considered as the driving
force for photochemical and photobiological events, such as
chem- and bioluminescence of cyclic peroxides, the isomer-
ization of retinal protonated Schiff bases, and the radiationless
deactivation of DNA bases.
Nonadiabatic transitions are ubiquitous in photochemistry
and photobiology, which are generally divided into two types
of internal conversion (IC) and intersystem crossing (ISC).
The former involves electronic states with the same spin
multiplicity, and the latter is a spin-forbidden process between
electronic states while altering spin. Generally speaking, the IC
and ISC processes take place in intersection regions of
potential energy surfaces (PESs) with larger probabilities.
Among the different types of intersections, conical intersection
exhibits its unique dynamic characteristics. Early in 1937,
Teller showed that conical intersection, initially defined as the
crossing point between two adiabatic electronic states of the
same space-spin symmetry, may be responsible for ultrafast
nonradiative transitions.5 After this seminal work, conical
intersection has become the subject of many theoretical
studies. Although it has been established theoretically that
conical intersection plays a key mechanistic role in photo-
chemistry, it was not until the end of the last century that the
importance of conical intersection was generally accepted by
experimental chemists. Over the past three decades, the IC
processes that occur on a time scale of picoseconds (ps) or
femtoseconds (fs) have been observed experimentally in a
number of chemical and biological systems with the develop-
ment of femtosecond time-resolved spectroscopy and ultrafast
X-ray diffraction techniques. Such a rapid IC process, which
cannot be explained with the traditional theories for avoided
crossings, provides clear evidence for the existence of conical
intersection. It should be noted that the nonadiabatic
transition in the vicinity of conical intersection is currently
understood by the measured decay rates of the radiative
population, the branching ratios of reaction channels, and the
yields of products in different states. Direct experimental
observation of nonadiabatic effects on a mechanism of the
photochemical reaction is still a challenging issue. In this case,
electronic structure calculations and nonadiabatic dynamics
Received: May 26, 2020
Accepted: August 7, 2020
Published: August 7, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.jpclett.0c01637

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The Journal of Physical Chemistry Letters
simulations exhibit their irreplaceable roles in exploring the
geometrical, topological, and dynamic features of the conical
intersection.
To date, a large number of studies have been devoted to the
conical intersection, and great progress have been made in its
basic theory, numerical algorithms, and applications in
different fields, which have been described in a few recent
reviews.6−8 As far as we know, most previous investigations
have focused on intersections of two electronic states.
However, the multistate intersection that involves more than
two adiabatic electronic states is common even in medium-
sized polyatomic molecules, and its mechanistic roles in
photochemistry are reflected in a large number of exam-
ples.9−16 Early in 2002, the three-state intersection (S1/T2/T1)
was discovered for a series of aromatic carbonyl com-
pounds.9−11,13 The existence of the S1/T2/T1 intersection
holds the key to understanding their excited-state relaxation
dynamics and provides a reasonable explanation why photo-
physical and photochemical properties of aromatic carbonyl
compounds were experimentally observed to be quite different
from those for aliphatic ketones. Martı ́nez and co-workers have
studied the excited-state intramolecular proton transfer of
malonaldehyde.12 Besides the in-plane proton transfer through
the two-state intersection, the minimum-energy intersection
(S2/S1/S0) of the lowest three states were observed to facilitate
the torsion along the C=C bond and the opening of the chelate
ring. The three-state intersection results in the very short
lifetime of S1 and increases the efficiency of the S2 → S1 → S0
deactivation. A four-state conical intersection related to the
O−O photolysis of an aromatic endoperoxide has been
reported by González and co-workers,14 which leads to an
ultrafast nonadiabatic transition (tens of femtoseconds) once
the aromatic endoperoxide is populated in the S2 or higher
excited state. Currently, the multistate intersection and its vital
role have emerged as a cutting-edge area of exploration in the
field of the photochemistry of polyatomic molecules. In this
Perspective, we first consider algorithms for searching
multistate minimum-energy intersection (MS-MEI), with an
emphasis on the latest developments in a general algorithm for
location of MS-MEI on the basis of electronic structure
calculation. The second part of this Perspective focuses mainly
on the crucial roles of multistate intersections in photo-
chemistry of polyatomic molecules, especially, how the state-
specific spin−orbit interaction controls the final state of the
ISC process that occurs in the MS-MEI region is described in
detail. In the third part of this Perspective, the combined
electronic structure calculation and nonadiabatic dynamics
simulation was demonstrated to be a practical strategy to
search different types of MS-MEI structures and to characterize
its mechanistic role in photodissociation dynamics for the
medium-sized or larger polyatomic molecules, which is
followed by an outlook at the end of this Perspective.
Algorithms for the MS-MEI Location. For a nonlinear
molecule containing N atoms, the minimum-energy inter-
section of multiple (M, M > 2) electronic states can be defined
as the point of (3N − 6)-dimensional space of nuclear
coordinates where the energy of the uppermost state is a
minimum under the constraint that all M states are degenerate.
Using the constrained minimization, Koga and Morokuma
reported the algorithm of Lagrange multiplier for locating the
minimum-energy intersection of two states with the aid of the
energy gradient.17 Then Yarkony and co-workers considered
the constraints based on quasi-degenerate perturbation
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It is necessary to characterize
multistate intersection in order to
fully understand mechanistic
photochemistry of medium-size
or larger polyatomic molecules.
Different algorithms have been
developed for location of the
three-state MEI structure. In par-
ticular, a general algorithm is
implemented on the basis of
electronic structure calculations,
which has been used to search
five- and six-state MEI structures
of 1,2-dioxetane, the simplest
intermediate involved in biolu-
minescence.
theory18,19 and defined the Lagrangian function to locate the
three-state MEI structures as follows
L(R, λ1 , λ 2 , λ3 , λ4 , λ5 , ξ) = EI + λ1(EI − EJ )
+ λ 2(EJ − EK ) + λ3HIJ + λ4HIK + λ5HJK + ξf (R)
(1)
where R denotes nuclear coordinates; EI, EJ, and EK are the
energies of the corresponding electronic states; HIJ, HIK, and
HKJ are the relevant elements of the configuration interaction
electronic Hamiltonian matrix(H); λ and ξ are Lagrange
multipliers, and f(R) denotes the optimal geometrical
constraints. The use of the Lagrange multiplier reduces the
three-state intersection to the stationary point of L(R, λ1, λ2,
λ3, λ4, λ5, ξ) function. The gradient of eq 1 with respect to the
independent R and multipliers is generally obtained by the
neglect of higher-order terms of the perturbation expansion,
which leads to the Newton−Raphson equation. Once energies,
energy difference gradients, nonadiabatic coupling vectors, and
the Lagrange Hessian for the relevant three states are
determined by electronic structure calculations, the New-
ton−Raphson equation can be solved iteratively until the
gradient of Lagrangian function vanishes.
The minimum-energy intersection of multiple electronic
states can be understood as the energy-minimum point of the
crossing seam of potential energy surfaces of these states. From
such an understanding, an unconstrained gradient projection
algorithm for searching the MEI structure on the crossing seam
of two states has been proposed by Robb and co-workers,20
which can be incorporated into an existing optimizer much
more easily compared with the Lagrange−Newton algorithm.
For the crossing seam of two states I and J with the same
space-spin symmetry, the energy difference gradient and
nonadiabatic coupling vectors, denoted as gIJ and hIJ, are of
great significance and the subspace spanned by the gIJ and hIJ
vectors is generally termed the branching plane (BP). The
remaining (3N - 8)-dimensional subspace is termed the
intersection space (IS). The degeneracy of the two states is
preserved at the first-order approximation if nuclear displace-
ment ΔR is orthogonal to the branching plane, i.e., satisfying
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Figure 1. Convergence process of the CAS(6,4)/6-31G(d) optimization for the five-state intersection of 1,2-dioxetane: (a) energies, (b) energy
gaps, (c) energy gradients, and (d) the optimized intersection structures of the lowest-lying five (MEI_5) and six (MEI_6) states as well the
equilibrium geometries of 1,2-dioxetane (1,2_Diox) and the biradical, along with bond lengths (Å) and the dihedral angle of Φ(O−C−C−O).

ΔR·gIJ = 0 and ΔR·hIJ = 0 simultaneously. The gIJ and hIJ
vectors are expressed as follows:
gIJ = c†I ∇R HcI − c†J ∇R HcJ
and
hIJ = c†I ∇R HcJ
The expansion coefficients of cI and cJ can be obtained by
solving the secular equation
(H − E I)c = 0
The following condition is fulfilled at all points on the
intersection space
2(EI − EJ )
GBP = gIJ = 0
|gIJ|
where (EI − EJ) rather than EI − EJ is minimized to approach
2
the crossing seam because it varies more smoothly around the
intersection region of two states. Meanwhile, the energy
gradient of the upper state J is projected into the intersection
space using the projection matrix P
T G IS = P∇R EM
P = I − ĝIJĝ TIJ − ĥIJ ĥ IJ
where the “hat” denotes the orthonormalized vectors. The
condition for minimization of energy in the intersection space
is as follows:
G IS = P∇R EJ = 0
It is important to realize that the projection algorithm is
designed to ensure that the gradient in the branching plane
(GBP) is orthogonal to the nuclear displacement or the
projected gradient (GIS) within the intersection space.
Very recently, the unconstrained gradient projection
algorithm has been generalized by us for optimizing the MEI
geometry of multiple states. For M adiabatic electronic states
(2) of the same spin multiplicity, there are M − 1 energy difference
gradients and M(M − 1)/2 nonadiabatic coupling vectors. The
composite energy-difference gradient within the branching
(3) plane (GBP) serves to minimize the energy gaps as
M−1
2(EM − EI )
GBP = ∑ gMI
I=1
α (8)
(4) where α is designed as a parameter that scales energy units and
reduces the step size of optimization. To ensure that GBP is
orthogonal to the nuclear displacement within the intersection
space at the first-order approximation, the projection matrix of
multistate intersection is defined as
(5) M−1 M−1 M
T
P=I− ∑ gM̂ Iĝ TM I − ∑ ∑ ĥIJ ĥ IJ
I=1 I=1 J=I+1 (9)
Then, the energy gradient of the uppermost state M is
projected to the intersection space using the projection matrix,
leading to the projected gradient (GIS)
(10)
(6)
The condition for minimization of the energy gaps within the
branching plane and for minimization of energy of the
intersection space is fulfilled when GBP in eq 8 and GIS in eq
10 vanish.
As can be seen from eqs 2−10 and the associated elucidation
(7)
above, the potential energies, energy gradients, and non-
adiabatic coupling vectors required in the unconstrained
algorithm can be obtained directly by means of multireference
configuration interaction calculations. When state I and J have
different multiplicities, the nonadiabatic coupling vector hIJ in
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eq 3 becomes zero, because the pure-spin wave functions are
used for the MS-MEI location. Therefore, the unconstrained
algorithm can be employed to search for the MEI structure of
multiple states with the same or different spin multiplicities. In
the seminal work by Robb and co-workers,20 the unconstrained
algorithm has been used to locate the MEI structure between
the S0 and T1 states of benzene. It should be noted that the
unconstrained algorithm is used only for determination of the
MEI structure. Whether the nonadiabatic transition occurs
efficiently in the MEI region can be understood by non-
adiabatic dynamics simulation that will be discussed below.
As the simplest system for understanding bioluminescence,
1,2-dioxetane has been extensively studied experimentally and
theoretically. It has been generally accepted that the
asynchronous-concerted cleavage of the O−O and C−C
bonds is the most probable mechanism for the thermal
decomposition of 1,2-dioxetane to produce the excited-state
formaldehyde that is responsible for bioluminescence.21 From
a molecular-orbital perspective, four configurations were
expected to be involved in the region of biradical produced
by the O−O cleavage of 1,2-dioxetane. Here we take 1,2-
dioxetane as a representative system to illustrate the
convergence characteristics and reliability of the unconstrained
gradient projection algorithm in the optimization of the MEI
structures of the lowest five and six electronic states. The
optimizations start from the S0 equilibrium geometry of 1,2-
dioxetane and have been performed with the standard
optimizer of BFGS implemented in Molpro 2012 software
package. As shown in Figure 1a,b, the energy gaps among the
lowest five (S2, S1, S0, T2, and T1) states are large at the starting
geometry. After the initial 10 iterations, however, the five states
are quasi-degenerate. More importantly, the energies of the five
states and the composite gradients change dramatically in this
initial phase of the optimization. As expected, the energy-
difference gradient (GBP) is responsible for minimizing the
energy gaps and should play a decisive role in the initial phase.
Accordingly, the nuclear displacement changes mainly within
the branching plane. Once the five states become degenerate or
quasi-degenerate, the nuclear displacement should be adjusted
within the intersection space, in order to converge to a
minimum on the crossing seam. As a result, the O−O bond of
1,2-dioxetane is suddenly broken, which is accompanied by a
large structural relaxation, and the composite gradient is
dominated by the projected gradient (GIS). The above analysis
and discussion are consistent with the dramatic changes of the
energies, energy gaps, and gradients in the initial phase.
In the subsequent 70 iterations, GBP does not vanish
completely, and the energy gaps fluctuate a little in this
transition phase. Meanwhile, GIS is not monotonously
decreased toward zero. This is due to the fact that the ground-
and excited-state potential energy surfaces are very flat in the
biradical region. Finally, the optimization converges to the
MEI structure of the five states, termed MEI(S2/S1/S0/T2/T1)
or MEI_5. Analogously, the MEI structure of the lowest six
states, MEI(S3/S2/S1/S0/T2/T1) or MEI_6, is determined in
the biradical region. As shown in Figure 1d, MEI_5 and
MEI_6 are similar to each other in structure.
The MEI_5 structure originates mainly from the σoo → σoo
and n0 → σoo* excitations of 1,2-dioxetane. The electronic wave
function of the MEI_5 structure is dominated by four
electronic configurations where the lone pair and unpaired
electrons are distributed in different p orbitals of the two
oxygen atoms. Because the MEI_5 structure is of a biradical
pubs.acs.org/JPCL Perspective
character, the triplet state is the lowest in energy and plays an
indispensable role in this intersection structure. The elongation
of the C−C bond in the MEI_5 and MEI_6 structures in
comparison with the structures of 1,2-dioxetane and the
biradical is consistent with the asynchronous-concerted
cleavage of the O−O and C−C bonds. In addition, the
carbonyl groups in MEI_5 or MEI_6 are similar to the
T1(3nπ*) and S1(1nπ*) states of formaldehyde in structure.
Formaldehyde can be produced either in the S0 state or the
excited T1(3nπ*) and S1(1nπ*) states through the MEI_5
region, while the luminescence of 2-dioxetane and its
derivatives originate from the two excited states.21 From the
above discussion, it can be expected that the multistate
intersections provide a thermal route to the excited state of
formaldehyde and may play an important role in the
nonadiabatic bioluminescent processes.
Before ending this subsection, we pay a little attention to a
simple algorithm that utilizes penalty function, which avoids
using nonadiabatic coupling vectors and Hessian matrix. The
penalty function algorithm was first introduced by Ciminelli,
Granucci, and Persico for the intersection optimization of two
electronic states.22 It was then modified by Levine, Coe, and
Martı ́nez for locating two- and three-state intersection of a
molecule in the gas phase.23 The objective function is defined
as the sum of the two-state averaged energy and a penalty
function
EI + EJ σ(EI − EJ )2
FIJ (R , σ , α) = +
2 (EI − EJ ) + α (11)
where α and σ are predetermined parameters. The use of
penalty function can suppress the energy gap of two relevant
states, leading to a decrease of the energy gap to a set
threshold. Recently, the penalty function algorithm was
implemented by Liu, Cui, and Fang in the framework of the
combined quantum mechanics and molecular mechanics
(QM/MM),24 which has been used to locate MEI structures
of multiple states for a few polyatomic molecules in the
aqueous solution. Finally, it should be noted that the penalty
function algorithm cannot ensure that the optimized
intersection structure is a minimum of the crossing seam and
an accidental intersection is sometimes determined, which
does not allow efficient nonadiabatic transition.
State Selectivity of Intersystem Crossing in the MS-MEI Region.
As noted before, internal conversion or intersystem crossing
can take place in the intersection region of two states of the
same or different spin multiplicities. However, the situation is
more complicated for a multistate intersection. If a multistate
intersection is correlated to M (M > 2) states of the same spin
multiplicity, it can serve as funnels for M(M − 1)/2 possible
IC processes. The probabilities that these IC processes occur
in the region of this multistate intersection are mainly
determined by the nonadiabatic coupling and vibronic
interaction of the associated states. However, the lowest-lying
state is finally populated, because these IC processes proceed
usually on a picosecond time scale. The combined electronic
structure calculation and nonadiabatic dynamics simulation has
* been recognized as the right way to ascertain such a multistate
intersection and the related dynamics, which will be discussed
in the next section. When a multistate intersection originates
from M states of different spin multiplicities, several ISC and/
or IC processes may occur in the M-state intersection region.
In the cases that the ISC processes are not in competition with
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Both internal conversion and
intersystem crossing can occur in
the same MS-MEI region. Unlike
the IC process where the non-
adiabatic coupling vector plays
an important role, the ISC process
is to a large extent determined by
the SOC interaction. In particular,
which state is finally populated is
controlled by the state-specific
SOC interaction. The state selec-
tivity of intersystem crossing that
occurs in the MS-MEI region
depends on not only the relative
energies of the relevant singlet
and triplet states but also the
properties of these states.
the IC process, the M-state intersection of different spin
multiplicities is equivalent to the intersection of two or more
states of the same spin multiplicity. Unlike the IC process, the
ISC process that occurs in the MS-MEI region exhibits unique
characteristics, which is tightly related to the spin−orbit
interaction. Which state is finally populated by intersystem
crossing depends on not only the relative energies of the
relevant states but also the properties of these states.
As a typical representative of polyatomic molecules,
photochemistry of aromatic carbonyl compounds has been
explored by means of electronic structure calculations,9−11,13
which reveals the importance of intersystem crossing in the
three-state intersection region. As listed in Table 1, the
calculated adiabatic excitation energies from the ground state
(S0) to the lowest-lying four excited states (S1, T1, S2, and T2)
are in excellent agreement with the band origins inferred
experimentally, which provides sufficient justification for the
reliability of ab initio method used. Because of the conjugated
interaction between the aromatic ring and carbonyl group,
several excited electronic states, such as S1(1nπ*), T1(3nπ*),
and T2 (3ππ*), are close to each other in energy. The
minimum-energy intersection of the three states (S1, T2, and
T1) was definitely determined, denoted as S1/T2/T1 hereafter.
Actually, the three-state S1/T2/T1 intersections have been
discovered to be common for a wide variety of aromatic
carbonyl compounds.9−11,13
Table 1. Adiabatic Excitation Energies (eV) for C6H5CHO and C6H5COCH3
C6H5CHO
a b c d
exp. CASSCF MCSCF CASPT2
S0 0.0 0.0 0.0 0.0
T1 3.12 3.13 3.07 3.07
S1 3.34 3.29 3.29 3.27
T2 3.30 3.22 3.08 3.16
S2 4.36 4.58 4.46 4.00
a
Experimental values. bThe CASSCF/6-31G(d) calculated values. cThe MCSCF/6-311G(d,p) calculated values. dThe CASPT2 calculated values.
e
The MCQDPT calculated values.
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A cleavage of α-bond and 1,5-H shift are two typical
reactions of a carbonyl compound, traditionally termed
Norrish type I and II reactions, respectively. For aliphatic
carbonyl compounds, Norrish type I and II reactions can take
place on the S1(1nπ*) state. However, the two types of
reactions occur only along the T1(3nπ*) pathway for most of
aromatic carbonyl compounds. In addition, aromatic carbonyl
compounds are highly phosphorescent molecules and usually
have shorter S1 lifetime in comparison with aliphatic carbonyl
compounds. The three-state S1/T2/T1 intersections hold the
key to understanding the unique excited-state behavior of
aromatic carbonyl compounds.
From the S1(1nπ*) state, there are two possible ISC
processes: S1(1nπ*) → T1(3nπ*) and S1(1nπ*) → T2(3ππ*).
According to the El-Sayed rule, the radiationless transition
between electronic states of different spin multiplicities usually
needs a simultaneous change in spin and orbital angular
momentums. As a result, the SOC interaction between S1 and
T1 state is very weak even in the vicinity of the S1/T2/T1
intersection. However, the situation is different for the S1 → T2
process in which a change in spin angular momentum can be
compensated by a change of orbital angular momentum. The
first-order SOC interaction between S1 and T2 is relatively
strong, which makes the S1 → T2 transition the dominant ISC
process despite the relatively low energy for the T1 state. In
addition, the state-specific SOC interaction leads to the
equilibrium structure of T2(3ππ*) as a stable biradical. The
T 2 ( 3 ππ*) equilibrium structures of benzaldehyde and
acetophenone, which are optically dark, have been determined
for the first time by means of experimental methodology of
ultrafast electron diffraction.25−27
It should be realized that the IC process from T2 to T1
proceeds with high efficiency in the S1/T2/T1 region, and the
time scale for this IC process is widely accepted to be on the
order of a vibrational period (several picoseconds). Therefore,
the T2 state acts as a bridge and the T1 structure is efficiently
produced via the sequential S1 → T2 → T1 processes in the
vicinity of the three-state S1/T2/T1 intersection. As shown in
Figure 2, the two unpaired electrons are distributed in the
phenyl ring of the T2 structure. As a result, the T2(3ππ*) state
is unreactive in view of α-bond cleavage and 1,5-H shift. In
contrast, the T1(3nπ*) state has the two unpaired electrons
localized in the carbonyl group and thus is the precursor state
for Norrish type I and II reactions and for phosphorescence
emission. The existence of the S1/T2/T1 intersection and the
associated state-specific SOC interaction for aromatic carbonyl
compounds explain clearly why their photophysical and
photochemical properties are quite different from those for
aliphatic carbonyl compounds.
C6H5COCH3
e a b
MCQDPT exp. CASSCF MCSCFc MCQDPTe
0.0 0.0 0.0 0.0 0.0
3.09 3.20 3.20 3.17 3.18
3.39 3.38 3.35 3.31 3.38
3.12 3.27 3.11 3.18
4.09 4.39 4.59 4.47 4.13
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calculated wave functions and the distribution of the unpaired

electrons.
As can be seen from Table 2, the six excited states are close
in energy, and most of these excited states are degenerate or
quasi-degenerate. Thus, the IC processes among the excited
states of the same spin multiplicity can take place very easily,
while the ISC process is to a large extent determined by the
SOC interaction between the relevant singlet and triplet states.
The S2(1ππ*) state that originates from π → π* one-electron
excitation is optically bright and should be populated upon UV
irradiation. Qualitatively, the SOC interaction is very weak
between S2(1ππ*) and T1(3ππ*), while the SOC interaction
between S1(1nSπ*) and T1(3ππ*) is relatively strong, which are
supported by the calculated SOC constants (∼2.0 vs 120.0
Figure 2. Excited-state electronic structures and decay pathways to cm−1). In addition, the S2(1ππ*) → T2(3nSπ*) and S2(1ππ*)
the T1 state for a class of aromatic carbonyl compounds. → T3(3nOπ*) ISC processes can proceed with considerable
probability because of the existence of the first-order SOC
interaction between S2(1ππ*) and T2(3nSπ*) or T3(3nOπ*).
As widely used photosensitizers in photodynamic therapy Considering the calculated SOC constants that agree
and the essential units of photo-cross-linking reactions in excellently with the El-Sayed rule (see Table 2), Cui and
structural biology, sulfur-substituted bases of nucleic acid Fang proposed three possible multistate pathways to the
(thiobases) have been the subject of numerous experimental T1(3ππ*) state, S2 → S1 → T1 (I), S2 → T2 → T1 (II), and S2
and theoretical studies.28−37 Currently, multistate intersections → T3 → T2 → T1 (III). Meanwhile, the efficiency for
and state-specific SOC interaction in a multistate quasi- formation of the T1 state is in the order (I) > (II) > (III) in
degenerate region have been recognized as key to under- view of the state-specific SOC effect.30
standing ultrahigh quantum yield of intersystem crossing to the In order to scrutinize the excited-state relaxation pathways
lowest triplet state (T1) for many different thiobases. Here we predicted by the CASPT2//CAS(16,11) calculations, 30
take 2-thiouracil as a representative to reveal how the long- Pollum and Crespo-Hernández have carried out femtosecond
lived T1 state is effectively populated after UV irradiation of broadband transient absorption experiments for 2-thiouracil
thiobases. It should be noted that both IC and ISC have been and 2-thiothymine in different solvents,31 which shows that the
experimentally observed to be ultrafast processes (100−400 fs) S1 state acts as a doorway state in the ultrafast and efficient
for 2-thiouracil, 2-thiothymine, and 4-thiothymi- population of the T1 state upon UVA excitation. Meanwhile,
dine.28,29,31,35,36 Such ultrafast population of the T1 state the sequential kinetic model, S2 → S1 → T1, was used to
occurs probably prior to a structural deformation. Therefore, explain the excited-state dynamics observed experimentally for
the Cs symmetry (planarity) of 2-thiouracil in the S0 state is not 2-thiouracil and 2-thiothymine.
destroyed in the optimization of the excited-state structuraes.30 The nonplanar structures and their relative energies for 2-
The lowest-lying four singlet (S0, S1, S2, and S3) and three thiouracil in the excited states were determined using the
triplet (T1, T2, and T3) states have been determined for the CASPT2//CASSCF method.32 Although the optimized
first time by the combined CASPT2 and CASSCF calculations structures are different from those reported in the previous
with the active space composed of 16 electrons distributed in study,30 the same pathways, S2 → S1 → T1 (I) and S2 → T2 →
11 orbitals, termed CASPT2//CAS(16,11) hereafter.30 With T1 (II), were proposed for the ultrafast population of the T1
respect to the S0 minimum, the CASPT2//CAS(16,11) state upon UV excitation of 2-thiouracil. Further MS-CASPT2
calculated relative energies of the six excited states are listed calculations on the photoexcited 2-thiouracil have been carried
in Table 2, together with the SOC constants calculated at the out by Mai, Marquetand, and González.33 Because pyramid-
CAS(16,11) level. Meanwhile, the attributes of the S3, S2, S1, alization at the C atom of the thiocarbonyl group is considered
T3, T2, and T1 states have been clearly identified by the for the excited-state structures, the attributes of the T2, S1 and
T1 states are changed considerably, which strengthens the SOC
Table 2. Relative Energies and the Spin-Orbit Coupling interaction between the S1 and T2 states. As a result, the main
(SOC) Constantsa Reported for the Lowest-Lying Six relaxation pathway was determined to be S2 → S1 → T2 → T1
Excited States of 2-Thiouracil by the MS-CASPT2 calculations, while S2 → S1 → T1 (I) was
expected to be only a side channel. However, the subsequent
relative energies (eV) SOC constantsa (cm−1) nonadiabatic dynamics simulations implemented by the same
states character ref 30 ref 33 ref 32 ref 30 group indicate that pathway I plays a more important role in
S0 0.0 0.0 0.0 0.1 (S0/T1) efficient formation of the T1 state.34
T1 (3ππ*) 3.46 2.96−3.35 2.85 121.0 (S1/T1) Very recently, Garavelli and co-workers have explored the
T2 (3nsπ*) 3.76 0.4 (S1/T2) excited-state behaviors of 2-thiouracil and 2,4-dithiouracil in
T3 (3nOπ*) 3.81 0.0 (S1/T3) water by the combined sub-20 fs broadband transient
S1 (1nsπ*) 3.81 3.33−3.45 3.36 81.8 (S2/T2) absorption spectroscopy in the UV region and CASPT2/
S2 (1ππ*) 3.86 3.75−3.93 3.55 20.5 (S2/T3) MM calculations,29 which provides evidence that the planar
S3 (1nOπ*) 3.89 0.2 (S3/T3) and pyramidal pathways predicted theoretically30,32,33 are a
pair of parallel decay routes, leading to population of the T1
a
The SOC constants are calculated at the intersection structures given state of 2-thiouracil in a time scale of ∼170 fs. Meanwhile, the
in parentheses. quasi-degenerate S2(1ππ*), S1(1nSπ*), and T2(3nSπ*) states, as
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listed in Table 2, was suggested to be responsible for the
photoinduced absorption of 2-thiouracil around 350 nm.29
Despite many theoretical studies focusing on photophysical
processes of 2-thiouracil, the intersection structure of three or
more excited states has not been determined to date. Thus, we
attempt to search for multistate intersections on the planar and
pyramidal pathways with the unconstrained gradient projection
algorithm described before. The three-state intersection (S2/
S1/T2) is located on the planar pathway, which is similar to the
S2 minimum in structure. As shown in Figure 3a, the energy
Figure 3. Planar (a) and nonplanar (b) pathways for efficient
population of the T1 state, together with the SOC constants (cm−1) in
parentheses and the relative energies (eV) of the stationary and
intersection structures. In addition, three-state intersection structures
are shown with the key bond lengths (Å) and the dihedral angle of
Φ(NCNS) (degree) listed in these structures.
difference between S2/S1/T2 and S2 is 0.05 eV at the
CASPT2//CAS(16,14) level. It is evident that the relaxation
process from S2 to S2/S1/T2 takes place very easily. The SOC
constant between S2 (S1) and T2 is calculated to be 84.6 (0.4)
cm−1 at the S2/S1/T2 structure. Because the S2 → S1 internal
conversion via the S2/S1/T2 intersection is an ultrafast process,
both S2 → T2 and S1 → T2 ISC processes take place with little
possibility. As a result, the S2/S1/T2 intersection plays a role
similar to that of the S2/S1 intersection, leading to efficient
population of the S1 state by the S2 → S1 internal conversion.
In principle, both the IC and ISC processes can occur in any
intersection region of three or more states with different spin
multiplicities. However, if the ISC processes are not in
competition with the IC process in the multistate intersection
region, this multistate intersection is equivalent to intersection
of multiple states of the same spin multiplicity, where the IC
processes occur eventually.
Once the S1 state is populated, the subsequent S1 → T1 and
S1 → T2 ISC processes can occur through the planar three-
state intersection (S1/T1/T2) that is determined by the
CAS(16,11) optimization. Although the same energy barrier
of 0.24 eV has to be overcome for the two ISC processes, the
SOC constant between S1 and T1 (89.2 cm−1) is much larger
than that between S1 and T2 (0.1 cm−1) at the S1/T1/T2
structure, which proves that the S1 → T1 transition should be
the primary pathway. Upon UV irradiation of 2-thiouracil to
the S2 state, the most probable in-plane decay pathway to the
T1 state is illustrated in Figure 3a, which is actually the same as
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S2 → S1 → T1 (I) proposed in a previous study,30 except for
different intersections involved.
For comparison, the relative energies of the nonplanar
stationary and intersection structures reported by González
and co-workers33 are recalculated at the CASPT2//CAS-
(16,14) level. In addition, a new three-state intersection (S1/
T1/T2) is located on the nonplanar pathway from S1 to T1 by
the present calculation. The calculated relative energies and
SOC constants for the nonplanar pathways are summarized in
Figure 3b, from which it can be concluded that the two
nonplanar pathways, S2 → S1 → T2 → T1 and S2 → S1 → T1,
are responsible for efficient population of the T1 state. This is
consistent with the mechanism predicted by nonadiabatic
dynamics simulations.34
A comprehensive physical picture for the efficient population
of the long-lived T1 state has been provided by means of
electronic structure calculations and femtosecond broadband
transient absorption experiments. Upon UV irradiation of 2-
thiouracil to its bright S2 state, the subsequent S2 → T2 ISC is a
spin-forbidden process, which is not in competition with the S2
→ S1 IC via either the planar S2/S1/T2 or nonplanar S2/S1
intersection region. However, the final population of the T1
state is mainly determined by the SOC interaction. The direct
S1 → T1 ISC is the most probable pathway via the planar S1/
T1/T2 region, while the direct S1 → T1 and indirect S1 → T2
→ T1 are a pair of competitive pathways through the
nonplanar S1/T1/T2 and S1/T2 intersection regions, respec-
tively. In conclusion, it is the state-specific SOC effect on
intersystem crossing in the region of multistate intersection
that determines how the long-lived T1 state of 2-thiouracil is
populated with ultrahigh quantum yield, which seem to be a
general property for many different sulfur-substituted bases of
nucleic acid.
The combination of electronic
structure calculation and non-
adiabatic dynamics simulation
has been recognized as the right
way to ascertain the vital roles of
multistate intersections in pho-
tochemical reactions.
Role of MS-MEI in Photochemistry Uncovered Further by the
Nonadiabatic Dynamics Simulations. As discussed before,
multistate intersections, which are often considered as the
analogues of transition states for thermochemical reactions,
play an important role in understanding the mechanism of a
photochemical reaction. First, it should be noted that
multistate intersections constitute multidimensional seams. In
most cases, the MS-MEI structures are hardly speculated from
a chemical intuition, because they are far from the equilibrium
geometry. For a complex molecule, full characterization of the
MS-MEI structure is very difficult using solely electronic
structure calculation. More importantly, when irradiated by
ultraviolet or visible light, the molecule is populated in an
excited state with a great deal of excess internal energy. The
statistical distribution of this excess energy is usually prevented
on account of the very short lifetime of the excited state. In this
case, the nonadiabatic IC or ISC process can take place in the
vicinity of high-energy multistate intersections as well as some
quasi-degenerate regions. This kind of dynamic effect (the
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nonergodic behavior) cannot be well understood without
nonadiabatic dynamics simulation.
As mentioned above, the BO approximation is no longer
valid in the region of the multistate intersection. In principle,
the full time-dependent Schrödinger equation should be used
to describe the motion of both electrons and nuclei. However,
the insurmountable computational scaling for quantum
dynamics simulation of nuclear motion makes it unaffordable,
if not impossible, to explore nonadiabatic processes for the
medium-sized or larger polyatomic molecules. Thus, the
mixed-quantum-classical (MQC) scheme has been put forward
to deal with the nuclei classically but incorporate feedback
between the quantum and classical degrees of freedom.
Ehrenfest mean field (EMF) and trajectory surface hopping
(TSH) are the most popular MQC nonadiabatic dynamics
approaches. In the mean-field scheme, the nuclear motion is
governed by weighted averages of potential energy surfaces for
the relevant adiabatic states, and the weights are determined by
integrating electronic Schrödinger equation. In the TSH
scheme, however, the nuclei move adiabatically on a single
PES but are allowed to hop into another electronic state.
Despite the great success of MQC dynamics simulations,
special care should be taken in the presence of intersections.
On one hand, the mean-field approximation in the EMF
scheme makes more sense to describe the dynamic processes
around multistate intersections, while the TSH simulation
requires a large number of trajectories to reproduce the
population on multiple states. Furthermore, it has been
observed that the outcome of TSH is very sensitive to small
differences in the protocol, especially in the presence of high
density of states and different spin multiplicities.38 On the
other hand, the intersection is usually located in a narrow
range of potential energy surface. When the trajectory leaves
the intersection region, the nuclear motion in the EMF scheme
keeps on the weighted averages of PESs and thus encounters
the inappropriate combination of adiabatic states. The
decoherence effect should be considered at least approximately
to address this issue. Recently we developed a quantum
trajectory mean-field (QTMF) method to overcome the
limitation of the original EMF scheme.39−41 Inspired by the
quantum measurement, the damping and random terms are
introduced to the equation of motion of electronic density ρ(t)
i very similar to the equilibrium geometry of the S2 state.42
ρ (̇ t ) = − [H̃ , ρ(t )] + ∑ ΓIJ+[MIJ ]ρ(t )
ℏ I≠J
+ ∑ γIJF + γIJ′ /[MIJ ]ρ(t )ξIJ(t )
I≠J (12)
The first term on the right-hand side is the same as that in the
original EMF and TSH schemes, in which
HIJ̃ = EI δIJ − iℏṘ ·dIJ (13)
where dIJ is the derivative nonadiabatic coupling between state
I and J as
dIJ = ⟨Ψ|∇
I R ΨJ ⟩ (14)
ΨI and ΨJ are the electronic wave functions of the relevant
states. The second term on the right-hand side of eq 12 is a
damping term that describes the decoherence effect using the
Lindblad superoperator D as
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1 †
+[MIJ ]ρ(t ) = MIJ ρ(t )MIJ† − {MIJ MIJ , ρ(t )}
2 (15)
where
MIJ = |Ψ⟩⟨Ψ|
I I
− |ΨJ ⟩⟨ΨJ | (16)
The third one is a random term that accounts for the back-
action effect of the nuclear motion to the electrons using the
superoperator H as
/[MIJ ]ρ(t ) = MIJ ρ(t ) + ρ(t )MIJ† − tr[(MIJ + MIJ† )ρ(t )]
ρ (t ) (17)
Here ΓIJ, γFIJ,
and rγ′IJ denote different types of decoherence
rates and ξIJ denotes white noise. The nuclear motion is treated
classically under the average potential the same as that in EMF
MR̈ = −∑ ρII ∇R EI + ∑ dIJρJI (EI − EJ )
I I ,J (18)
where M is the diagonal mass matrix. In brief, the electronic
and nuclear motions in QTMF are governed by eqs 12 and 18,
respectively. The QTMF method captures the nonadiabatic
effect near the intersections and the decoherence effect in the
weak coupling region simultaneously, which is superior to the
original EMF scheme. In comparison with the most popular
TSH algorithm, QTMF is well-adapted to deal with non-
adiabatic transitions that occur in the vicinity of multistate
intersection.
Upon UV irradiation of acetylacetone, the second excited
singlet state (S2) is initially populated and the lowest three
singlet states (S2, S1, and S0) are at least involved in its
photoisomerization dynamics, which has been taken as an
example to perform the QTMF simulation.42 Although
acetylacetone is a prototype of β-diketones, it exists mainly
as the chelated enolic form, because of the intramolecular H-
bond coupled with a π-electronic delocalization over the O−
C−C−C−O pseudocycle backbone in the enolic structure.
Starting from the S2 Franck−Condon structure of the enolic
form, we attempt to optimize three- or two-state MEI structure
at the CASSCF level. However, only one MEI structure
between the S2 and S1 states is located by the CASSCF
optimization, denoted as S2/S1 hereafter. As shown in Figure
4a, the S2/S1 intersection has nonplanar structure, which is
Analogously, the sole S1/S0 intersection structure between S1
and S0 is determined by the CASSCF optimization, which
involves a large change in the O5−C4−C3−C2 dihedral angle
from 74.3°(72.6°) in the S2(S2/S1) structure to 103.3° in the
S1/S0 intersection. From the structural similarity between S2
and S2/S1 and a large intramolecular rotation from S2/S1 to S1/
S0, it might be expected that the S2 deactivation should follow
the pathway S2 → S2/S1 → S1 → S1/S0 → S0. However, more
important nonadiabatic transitions that involve different
intersection structures are uncovered by the QTMF simu-
lations, which will be discussed below.
Three hundred distinctive configurations in the S2 state were
initially generated by randomly sampling from the Wigner
distribution of harmonic vibrations of the S0 enolic structure
and then used for the QTMF nonadiabatic dynamics
simulations. Among the simulated 300 trajectories, however,
the S2 → S1 transitions that occur in the vicinity of the S2/S1
structure were observed in only 51 trajectories. It is evident
that the nonadiabatic transition in the S2/S1 region is not the
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Figure 4. Optimized MEI structures for photoisomerization of
acetylacetone, along with atom-numbering in panel a, the selected
bond lengths (Å), and two dihedral angles of Φ1(O1−C2−C3−C4)
and Φ2(O5−C4−C3−C2).
main deactivation pathway of the S2 state. Upon closely
examining the QTMF simulated results, it has been found that
more than 200 trajectories are propagated on the S2 state
within the initial 50 fs. During this initial period, the proton
shuttles between the two oxygen atoms, which is accompanied
by the S2 → S1 transition. A typical molecular structure was
extracted from these trajectories and used for the subsequent
optimization of the MEI structure. In this way, the second MEI
between S2 and S1 is finally located and denoted as S2/S1-dyn-1
hereafter. As shown in Figure 4c, the S2/S1-dyn-1 structure has
the C2V symmetry. Evidently, the S2 → S1 transition occurs
dominantly in the S2/S1-dyn-1 region. In addition, the third
MEI between S2 and S1 is located by the CASSCF optimization
using a snapshot extracted from the QTMF simulation as the
initial guess, termed S2/S1-dyn-2 in Figure 4d. Because the S2
→ S1 transition occurs in the S2/S1-dyn-2 region with a little
probability (∼1.0%), this structure is not reported in the
previous study.42
The strong coherence among the S2, S1, and S0 states occurs
in a very short period (∼100 fs), which is derived from time
evolution of the diagonal and the off-diagonal elements of the
density matrix for the QTMF simulated 23 trajectories. Upon
close examination of the simulated 23 trajectories, it was found
that the ultrafast S2 → S1 → S0 internal conversion occurs in
two structural regions that are identified in terms of the C−C
and C−O bond lengths, the Φ1(O1−C2−C3−C4) and
Φ2(O5−C4−C3−C2) dihedral angles, and the orientation of
the hydroxyl group. The QTMF simulations give a hint for the
existence of the three-state intersection, which is confirmed by
the optimization of the MEI structure on the basis of the initial
nuclear configuration from these dynamic trajectories. Two
MEI structures of the S2, S1, and S0 states were located by the
CASSCF optimizations, denoted as S2/S1/S0-dyn-1 and S2/S1/
S0-dyn-2. With respect to the S0 minimum, the relative energies
of the S2/S1/S0-dyn-1 and S2/S1/S0-dyn-2 structures are 93.7
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and 99.6 kcal/mol, respectively, at the CASPT2//SA3-
CAS(10,9)/6-31G(d) level. Without the QTMF simulation,
it would be very difficult to search for all of these MEI
structures from a chemical intuition.
Different spectroscopic and imaging techniques have been
employed to explore photodissociation reactions of small
molecules containing heteroatom, such as phenol, thiophenol,
thioanisole, thiophene, thiophenone, furanone, and their
derivatives. The intersection between the 1ππ* and 1πσ*-
(1nσ*) excited states has been recognized as key to
understanding the detailed mechanism of these photoreac-
tions.43,44 We have taken 2(5H)-thiophenone (2TP) as a
representative of these heteroatom-containing molecules and
performed the combined QTMF and MM (QTMF/MM)
nonadiabatic dynamics simulations to study its photodissoci-
ation in CH3CN.43 Among the QTMF/MM-simulated 448
reactive trajectories, the nonadiabatic transition from 1ππ* to
1
πσ* was observed in only the 14 trajectories. The QTMF/
MM simulation reveals that the nonadiabatic transition occurs
in the 1ππ*/1πσ* region with little probability (∼0.03), and
the 1ππ*/1πσ* intersection plays only a minor role in the
photoinduced ring-opening reaction of 2(5H)-thiophenone,
which is quite different from the mechanism proposed
experimentally.44,45
Upon careful examining of the time evolution of the density
matrix and the related structural parameters for the remaining
434 trajectories, it was found that the S2(1ππ*) population is
nearly unchanged with a value of ∼1.0 even if the α−C−S
bond is completely broken. Obviously, the photoinduced ring-
opening reaction proceeds along the diabatic S2(1ππ*)
pathway with a probability of ∼0.97 and the dynamic effect
plays a crucial role in the mechanism of the ring-opening
reaction for 2TP in CH3CN. Given the bond parameters
extracted from the QTMF/MM trajectories, the S2/S1/S0, S2/
S1, and S1/S0 minimum-energy intersections were finally
located by the CASSCF optimizations (see Figure 5), and
Figure 5. Optimized MEI structures for ring-opening of 2(5H)-
thiophenone in CH3CN, along with selected bond lengths (Å).
their relative energies were calculated to be 75.7, 87.1, and 74.7
kcal/mol, respectively, at the QM[CASPT2//CAS(10,8)/6-
31G(d)]/MM level. These intersection structures are acces-
sible in energy upon irradiation of 2TP at ∼260.0 nm,45 which
corresponds to the vertical excitation larger than 100.0 kcal/
mol. More importantly, the QTMF/MM simulations reveal
that most of the nonadiabatic transitions from S2 to S0 occur
efficiently in the region of the S2/S1/S0 intersection, leading to
reformation of the parent molecule and the final product in the
S0 state. Their branching ratio was determined to be 1:2 by the
simulations.45
As described above, the MS-MEI structure determined by
electronic structure calculation is very helpful for analysis and
understanding of the QTMF simulated results. However, some
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MS-MEI structures that are related to the mechanism of a
photochemical reaction cannot be found on the basis of the
initial guess from a chemical intuition, because of the
complexity of multidimensional crossing seams. In this case,
the structural information extracted from the QTMF dynamics
simulation can be used as diverse initial guesses to search
different types of MS-MEI structures by further electronic
structure calculations, whereas these MS-MEI structures can
provide new mechanistic pathways for in-depth understanding
of the simulated results and for further improving the QTMF
simulation. Therefore, the combination of QTMF simulation
and electronic structure calculation is the right way to ascertain
the vital roles of multistate intersections in photochemical
reactions.
Summary and Outlook. There have been many theoretical
and experimental demonstrations for the crucial role of
multistate intersection in photochemistry and related fields.
Both the IC and ISC processes can occur in the vicinity of the
same multistate intersection, which is different from one-fold
nonadiabatic transition in the region of two-state intersection.
In particular for the ISC processes, the selective population of
the final state is controlled by the state-specific SOC
interaction, which depends mainly on the attribute of the
relevant states. A general algorithm has been implemented for
location of the MS-MEI structure, which has been successfully
used to search different types of MS-MEI structures for 1,2-
dioxetane and thiobases. Without diverse initial guesses from
nonadiabatic dynamics simulation, however, many critical MS-
MEI structures for a complex molecule cannot be located
solely by electronic structure calculations because of the
complexity of multidimensional intersection seams. Analo-
gously, the dynamic effect cannot be well described without
nonadiabatic dynamics simulation. Therefore, the interweaving
of electronic structure calculation and nonadiabatic dynamic
simulation is the right way to characterize the vital roles of
multistate intersections in photochemical reactions. Finally, it
should be noted that the cross-validation between theoretical
prediction and experimental evidence is very important to
understand the unique roles of multistate intersections in
photochemistry.
Despite the encouraging results on the characterization of
multistate intersections and their important roles in photo-
chemistry using the CASPT2//CASSCF calculations and the
QTMF simulations, there is still much room for further
development in this work. Before ending this Perspective, we
would like to discuss two issues in the field of nonadiabatic
dynamics simulation that are associated with multistate
intersections. When the f- or d-elements are involved in
photophysical and photochemical processes, such as the rare-
earth luminescent materials and precious metal catalysts, the
SOC interaction becomes very strong. In this case, the ISC
process has been experimentally observed to occur on a time
scale of picoseconds or even femtoseconds, which can be in
competition with the IC process. However, the MQC dynamic
approaches such as QTMF were originally developed to
simulate the IC process. The dynamic effect on ISC in the
vicinity of multistate intersections is difficult to describe
appropriately by the MQC dynamic simulation. In the
framework of spin-diabatic representation as used widely, the
conservation of total energy is violated during the QTMF
simulation, if the nuclei evolve on the mean field while the
motion of electrons is perturbed by the SOC interaction. To
the best of our knowledge, this cannot be remedied with an
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explicit form of force correction on the right-hand side of eq
18. The spin-adiabatic representation has been reported as an
alternative to simulate ISC processes using surface hopping.46
However, the gradient of energy that includes the SOC
interaction, which is required in the adiabatic representation, is
a nontrivial problem and still unavailable in most quantum
chemistry programs. On the basis of our recent work in
QTMF-FSSH,41 a generalized QTMF method to deal with
both the IC and ISC processes is under development now.
Another challenging issue originates from the growing of
dimensionality and the extension of time scale for realistic
photochemical processes. For example, high-accuracy elec-
tronic correlation methods should be used for reasonable
description of the excited-state behaviors of transition metal
complexes and the related calculations are very time-
consuming. Meanwhile, the SOC interaction is usually strong
in these complexes and the ISC processes occur on a time scale
of nanosecond or longer, which is still a challenging issue for
nonadiabatic dynamics simulation. Therefore, it is extremely
difficult to search the MS-MEI structures and to simulate the
nonadiabatic transitions in the MS-MEI region for complex
photochemical systems by using high-accuracy electronic
correlation methods. A possible method is to develop and
apply more efficient computational models with relatively low
accuracy. A semiempirical method, such as OM2/MRCI, and a
sophisticated force field, such as a machine learning model, are
good candidates. In addition, the application of elaborate
biases on simulations, for example, the bias potential in
metadynamics,47 the scaled nonadiabatic coupling in TSH,48
and the artificial force in the global reaction route mapping,49
may provide another attractive solution not only to search
intersections automatically but also to cover a broad range of
time scales for radiationless deactivation. This can be expected
to bring more opportunities to investigate multistate
intersections and the related IC and ISC processes more
effectively.
■
AUTHOR INFORMATION
Corresponding Author
Wei-Hai Fang − Key Laboratory of Theoretical and
Computational Photochemistry of Ministry of Education,
College of Chemistry, Beijing Normal University, Beijing
100875, P.R. China; orcid.org/0000-0002-1668-465X;
Email: fangwh@bnu.edu.cn
Authors
Lin Shen − Key Laboratory of Theoretical and Computational
Photochemistry of Ministry of Education, College of Chemistry,
Beijing Normal University, Beijing 100875, P.R. China;
orcid.org/0000-0001-6878-8963
Binbin Xie − Hangzhou Institute of Advanced Studies, Zhejiang
Normal University, Hangzhou 311231, Zhejiang, P.R. China
Ziwen Li − Key Laboratory of Theoretical and Computational
Photochemistry of Ministry of Education, College of Chemistry,
Beijing Normal University, Beijing 100875, P.R. China
Lihong Liu − Key Laboratory of Theoretical and Computational
Photochemistry of Ministry of Education, College of Chemistry,
Beijing Normal University, Beijing 100875, P.R. China
Ganglong Cui − Key Laboratory of Theoretical and
Computational Photochemistry of Ministry of Education,
College of Chemistry, Beijing Normal University, Beijing
100875, P.R. China; orcid.org/0000-0002-9752-1659
Complete contact information is available at:
https://dx.doi.org/10.1021/acs.jpclett.0c01637
J. Phys. Chem. Lett. 2020, 11, 8490−8501
The Journal of Physical Chemistry Letters
https://pubs.acs.org/10.1021/acs.jpclett.0c01637
Notes
The authors declare no competing financial interest.
Biographies
Lin Shen received his Ph.D. degree in Chemistry under the
supervision of Prof. Wei-Hai Fang at Beijing Normal University in
2012. He continued his research as a postdoctoral associate with Prof.
Hao Hu at the University of Hong Kong and Prof. Weitao Yang at
Duke University. He has been an associate professor in the College of
Chemistry at Beijing Normal University since 2018. His current
research focuses on methodology development for multiscale
nonadiabatic dynamics combined with machine learning and
enhanced sampling techniques to provide new computational tools
in photochemistry and photobiology.
Binbin Xie received his Ph.D. degree in Chemistry under the
supervision of Prof. Wei-Hai Fang at Beijing Normal University in
2017. Currently he is a research assistant at Hangzhou Institute of
Advanced Studies at Zhejiang Normal University. His research
focuses on understanding diverse photophysical and photochemical
processes varying from small molecules to large biological systems by
using electronic structure calculations and nonadiabatic dynamic
simulations.
Ziwen Li is currently a Ph.D. student at the Beijing Normal
University, supervised by Prof. Ganglong Cui. His research focuses on
the development of a general algorithm for searching minimum-
energy intersection of multiple electronic states.
Lihong Liu earned her B.S. and Ph.D. degree in Chemistry from
Beijing Normal University in 2008 and 2014, respectively. She has
been an associate professor in the College of Chemistry at Beijing
Normal University since 2017. Currently, her research interests focus
on ab initio nonadiabatic dynamics simulations of photoinduced
chemical and biological processes.
Ganglong Cui got his B.S. degree in Chemistry from Beijing Normal
University in 2004. He further studied theoretical chemistry under the
supervision of Prof. Wei-Hai Fang at Beijing Normal University and
Prof. Weitao Yang at Duke University and got his Ph.D. degree in
Theoretical Chemistry in 2009. He continued his research as a
postdoctoral associate with Prof. Weitao Yang at Duke University
from 2010 to 2011 and as an Alexander von Humboldt Foundation
Scholar with Prof. Walter Thiel at Max-Planck-Institut fü r
Kohlenforschung from 2011 to 2014. Then, he joined College of
Chemistry in Beijing Normal University and became a full professor
in 2014. His present research interests are mainly focused on
developing and applying accurate and efficient excited-state electronic
structure and ab initio nonadiabatic dynamics methods for simulating
photophysical and photochemical processes in complex chemical,
biological, and materials systems.
Wei-Hai Fang is professor of chemistry at Beijing Normal University.
He leads a research team engaged in studying theoretical and
computational photochemistry.
■ ACKNOWLEDGMENTS
We are grateful to financial support from the NSFC for W.-
H.F. (Grant Nos. 21590801, 21688102, 21520102005, and
21421003), L.S. (21903005), and B.X. (21903068).
■
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