Quantum optimal control of electron ring currents in chiral aromatic molecules

Manabu Kanno, Kunihito Hoki, Hirohiko Kono, and Yuichi Fujimura

Citation: The Journal of Chemical Physics 127, 204314 (2007); doi: 10.1063/1.2806180
View online: http://dx.doi.org/10.1063/1.2806180
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 THE JOURNAL OF CHEMICAL PHYSICS 127, 204314 共2007兲

Quantum optimal control of electron ring currents in chiral

aromatic molecules
Manabu Kanno, Kunihito Hoki, Hirohiko Kono, and Yuichi Fujimuraa兲
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
共Received 17 August 2007; accepted 15 October 2007; published online 30 November 2007兲

We report the results of optimal control simulations of ␲-electron rotation 共ring current兲 in a
six-membered chiral aromatic molecule, 2,5-dichloro关n兴共3,6兲pyrazinophane 共DCP兲, attached at a
surface and excited by a linearly polarized UV laser. DCP has a pair of optically allowed,
quasidegenerate ␲-electronic excited states. The laser pulse to generate an approximate angular
momentum eigenstate consisting of the quasidegenerate states was designed using the global
optimal control theory. For both counterclockwise and clockwise ␲-electron rotations, the calculated
objective functional and target yield as a function of the angle of the photon polarization vector
show two maxima and two minima. The origin of the two minima is coherent excitation to only one
of the quasidegenerate states. The two maxima arise from creation of a superposition of the
quasidegenerate states. The optimal control pulse at the maxima is a two-color laser field resonant
with the quasidegenerate states. The electric field of the optimal control pulse consists of two parts:
a slowly oscillating part with phase ␸env and a rapidly oscillating one. The phase ␸env is a crucial
parameter for determination of the rotation direction of ␲ electrons at the end of control. The results
of the optimal control simulations suggest that ␲-electron rotation can be controlled by applying a
two-color laser field with adjusted phases. © 2007 American Institute of Physics.
关DOI: 10.1063/1.2806180兴

I. INTRODUCTION Barth et al. carried out a quantum simulation of electron

Rapid progress in laser technology in recent decades has
enabled control of various laser parameters. Progress has
been made in ultrashort pulse generation through pulse com-
pression, and the available wavelength range has been ex-
panded. The amplitude and phase of laser fields can now be
adjusted as desired by means of pulse shaping techniques.
Accordingly, precise quantum control of molecular motions
is becoming a reality. Results of a number of experimental
and theoretical works on manipulation of nuclear motions in
molecules by using laser pulses on a time scale of several
tens of femtoseconds to picoseconds have been reported.1 On
the other hand, a UV/visible attosecond/several-femtosecond
laser pulse is expected to make it possible to control intramo-
lecular electron dynamics in an ultrashort time regime in
which nuclear degrees of freedom can be ignored. For in-
stance, results of experiments on electron localization in the
dissociation process of the deuterium molecular ion D+2 by
linearly and circularly polarized few-cycle laser pulses have
been presented.2 As for theoretical work, simulations of
charge transfer, i.e., switching of permanent electric dipoles,
of lithium cyanide LiCN by linearly polarized laser pulses
have been performed.3 These studies, however, dealt with
simple-structured few-atom molecules. Control of electron
motions in polyatomic molecules or molecular assemblies is
needed for the development of molecular functionality. In
particular, methods to induce and control electric currents in
molecular devices are essential for nanotechnology.
a兲
Electronic mail: fujimurayuichi@mail.tains.tohoku.ac.jp
dynamics in polyatomic molecules and showed that ␲ elec-
trons of an aromatic molecule, Mg porphyrin, can be rotated
along its ring by using a circularly polarized laser pulse.4 In
this case, ring currents are induced with a combination of an
achiral molecule and chiral light, and the rotation direction
of ␲ electrons is predetermined by that of the polarization
plane of the applied pulse. That is, chirality of a laser pulse is
transferred to a directional ring current.
For eliciting productive functions of molecular devices,
directionality intrinsic to the molecule, not to light, should be
provided to electric currents. In this context, we have dem-
onstrated that ␲ electrons in a chiral aromatic molecule can
be rotated along its ring by using a linearly polarized laser
pulse.5 This indicates that molecular chirality can also be a
source of directional ring currents because a nonhelical pho-
ton has no angular momentum. ␲-electron dynamics reflects
the asymmetry of the molecule itself. In Ref. 5, we have
shown that the rotation direction of ␲ electrons depends on
the polarization direction of the applied pulse relative to the
spatial configuration of each enantiomer on the basis of a
three-level model analysis. However, the abovementioned
pulse-design scheme is valid only for an ultrashort linearly
polarized single-peaked laser pulse, e.g., a sin2 or Gaussian
pulse such as we have used in the numerical simulations in
Ref. 5. It is not clear yet what are the significant factors for
determination of the rotation direction without restriction on
the envelope of a laser field.
In this article, we report the results of optimal control
simulations of ␲-electron rotation 共ring current兲 in a chiral
aromatic molecule. The optimal control theory 共OCT兲 is a

0021-9606/2007/127共20兲/204314/9/$23.00 127, 204314-1 © 2007 American Institute of Physics

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 204314-2 Kanno et al. J. Chem. Phys. 127, 204314 共2007兲

TABLE I. Hückel MO energies of ␲ orbitals of DCP calculated by solving

the secular equation.

␲ orbital Orbital energy 共eV兲

兩4bg典 4.31
兩4au典 2.25
兩3au典 共LUMO兲 1.56
兩3bg典 共HOMO兲 −2.44
兩2bg典 −3.23
兩2au典 −4.55
兩1bg典 −5.11
兩1au典 −5.74

FIG. 1. S and R enantiomers of DCP. The directions of transition dipole

moments 具9兩␮ ˆ 兩0典 and 具10兩␮
ˆ 兩0典 of an R enantiomer are shown as well as
those of photon polarization vectors e± defined as 具9兩␮ ˆ 兩0典 · e± Then, DCP is regarded as being of C2h symmetry and having
= ± 具10兩␮
ˆ 兩0典 · e±. The magnitudes of 具9兩␮ ˆ 兩0典 and 具10兩␮
ˆ 兩0典 are 2.02ea0 and
eight pz orbitals and ten ␲ electrons in this description of
1.63ea0, respectively.
␲-electron dynamics. The first term in Eq. 共1兲 gives the one-
electron energy and hlm is the hopping integral. The second
powerful mathematical tool for designing an optimal control and third terms in Eq. 共1兲 represent the on-site and long-
pulse to lead a quantum system to a desired target state.6–9 range electron-electron repulsions, respectively. U is the so-
Here, we aim to obtain as much 共angular兲 momentum as called on-site Hubbard parameter. Several forms have been
possible for a unidirectional circular path along an aromatic proposed for the long-range repulsion parameter Vlm, and we
ring at the end of control by linearly polarized laser fields. assume the Ohno potential12
Optimal control simulation, which reveals the best wave pro-
file of a laser pulse for achieving a target state under a given U
Vlm = , 共2兲
constraint, is the most suitable approach to investigate how 关1 + 共Rlm/d兲2兴1/2
␲-electron rotation can be controlled in an efficient way with
where Rlm ⬅ 兩Rl − Rm兩, with nuclear coordinates Rm of the
an appropriate choice of laser parameters.
mth atom, and d is the unit bond length.
In the following sections, a chiral aromatic molecule
The diagonal elements of the hopping integral hlm are
with a six-membered ring, 2,5-dichloro关n兴共3,6兲pyrazino-
given by
phane 共DCP兲, is used as a system 共Fig. 1兲. The positive in-
teger n specifies the length of the ethylene bridge 共CH2兲n. hll = ␣l − 兺 Vlm , 共3兲
The value of n is set as n ⯝ 10 to prevent free rotation of the m
aromatic ring. DCP has quasidegenerate ␲-electronic excited
and the off-diagonal elements are assumed to have a nonzero
states, whose linear combinations give approximate angular
value only between nearest neighbors,

再 冎
momentum eigenstates for circulation of ␲ electrons along
the aromatic ring. The molecule is assumed to be preori- ␤lm 共兩l − m兩 = 1兲
ented, e.g., fixed to a surface by the ethylene bridge, and all hlm = 共4兲
0 共兩l − m兩 艌 2兲.
nuclei in the molecule are treated as frozen.
Here, ␣l and ␤lm are determined as

II. THEORY
␣ l = ␣ + ␨ l␤ , 共5a兲

A. Effective Hamiltonian formalism for ␲-electron ␤lm = ␩lm␤ , 共5b兲

dynamics
where ␣ is the Coulomb integral at a carbon atom and ␤ is
First of all, let us begin with a description of how to the resonance integral between the nearest carbon atoms. Pa-
evaluate the field-free ␲-electronic states of chiral aromatic rameters ␨l and ␩lm are introduced for evaluation of the in-
molecules. We employ the semiempirical Pariser-Parr-Pople tegrals for heteroatoms, halogen atoms, and carbon atoms
共PPP兲 model to express the effective ␲-electronic Hamil- adjacent to them.
tonian Ĥ␲, For U = 0, the second and third terms in Eq. 共1兲 vanish
hlmâl†␴âm␴ + U 兺 n̂m␣n̂m␤ + 兺 and one obtains hll = ␣l. The PPP Hamiltonian Ĥ␲ is then
Ĥ␲ = 兺
l,m,␴
Vlmn̂l␴n̂m␴⬘ ,
reduced to the Hückel Hamiltonian ĤHMO.13 In order to ob-
m l⬎m,␴,␴⬘
tain eigenstates of Ĥ␲, we first calculate those of ĤHMO. Pa-
共1兲
rameters for the one-electron energy are set as employed for
where †
âm is a creation operator of a ␲ electron in a pz
␴ linear polyenes:11 ␣ = 0 and ␤ = −2.40 eV. The standard val-
orbital at the mth atom 兩␹m典 with a spin ␴, and n̂m␴ ues presented by Streitwieser14 are adopted for ␨l and ␩lm:
⬅ âm
†
␴âm␴. With a proper choice of parameters, the PPP ␨N = 0.5, ␨Cl = 2, ␨C = 0.2 共only for carbon atoms adjacent to a
model is known to be capable of reproducing various optical chlorine atom兲, ␩CCl = 0.4, and for the other atoms and bonds,
properties of ␲-conjugated systems.10,11 The effect of the ␨l = 0 and ␩lm = 1. Orbital energies and linear combination of
nonaromatic ethylene bridge is neglected in the PPP model. atomic orbital 共LCAO兲 coefficients of eight ␲ orbitals of
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 204314-3 Ring currents in chiral aromatic molecules J. Chem. Phys. 127, 204314 共2007兲

TABLE II. Properties of optically allowed ␲-electronic excited states of which transition energies from the
ground state 兩0典 = 兩1 1Ag典 are less than 10.0 eV. Weight is a square of a CI coefficient of each electronic
configuration.

Transition Oscillator Dominant electronic

Excited state energy 共eV兲 strength configurations Weight

兩1典 = 兩1 1Bu典 4.31 3.46⫻ 10−1 兩3bg典 → 兩3au典 0.662

兩2bg典 → 兩4au典 0.211

兩2典 = 兩2 1Bu典 5.05 8.52⫻ 10−2 兩3bg典 → 兩4au典 0.528

兩2bg典 → 兩3au典 0.382

兩4典 = 兩3 1Bu典 6.66 1.00 兩1bg典 → 兩3au典 0.605

兩2bg典 → 兩4au典 0.169

兩7典 = 兩4 1Bu典 7.07 1.05 兩1bg典 → 兩4au典 0.340

兩2bg典 → 兩3au典 0.241
兩3bg典 → 兩4au典 0.138

兩9典 = 兩5 1Bu典 7.66 2.31 兩2bg典 → 兩4au典 0.334

兩1bg典 → 兩3au典 0.201
兩3bg典 → 兩4au典 0.167
兩2bg典 → 兩3au典 0.124

兩10典 = 兩6 1Bu典 7.77 1.51 兩1bg典 → 兩4au典 0.460

兩2bg典 → 兩3au典 0.144
兩2bg典 → 兩4au典 0.103

兩15典 = 兩7 1Bu典 9.79 2.29⫻ 10−3 兩2au典 → 兩4bg典 0.614

兩2au典 , 兩3bg典 → 兩3au典 , 兩4au典a 0.140
a
This double excitation consists of a singlet electron pair and a singlet hole pair 关Ref. 10共b兲兴.

DCP are obtained by solving the secular equation with over- ⳵

laps 具␹l 兩 ␹m典 = ␦lm 共Table I兲. The eigenstate of ĤHMO is repre- iប 兩⌿共t兲典 = Ĥ共t兲兩⌿共t兲典, 共8兲
⳵t
sented by a Slater determinant composed of LCAO–
molecular orbitals 共MOs兲. with the initial condition
Configuration interaction 共CI兲 is taken into account by
兩⌿共0兲典 = 兩0典, 共9兲
diagonalizing Ĥ␲ including all singlet single and double ex-
citations 共SDCI兲. The on-site Hubbard parameter U is set as where 兩0典 = 兩1 1Ag典 is the ground state. We solve Eq. 共8兲 by
in Ref. 11: U = 11.1 eV. The aromatic ring forms a planar expanding 兩⌿共t兲典 in terms of 17 singlet eigenstates of Ĥ␲
structure and we simply assume that the CC and CN bond with energy ប␻k ⬍ 10.0 eV 共␻0 = 0兲, which is a typical value
length is 1.40 Å, the CCl bond length is 1.80 Å, and of the first ionization energy of aromatic molecules, obtained
⬔NCCl= 120°. The unit bond length d is then 1.40 Å. Con- at the level of SDCI,
sequently, 136 singlet eigenstates of Ĥ␲, each of which is a 16
兩⌿共t兲典 = 兺 ck共t兲e−i␻kt兩k典.
linear combination of those of ĤHMO, are obtained by SDCI
共10兲
using 15 single and 120 double excitations 共Table II兲. k=0

B. Time evolution of ␲-electron wave packets By inserting Eq. 共10兲 into Eq. 共8兲, we derive the coupled
equations of motion for the expansion coefficients 兵ck共t兲其,
The time-dependent Hamiltonian of an aromatic mol-
ecule interacting with a classical laser field ␧共t兲 is expressed dck共t兲
16

in the dipole approximation and the length gauge as iប = − 兺 ck⬘共t兲ei共␻k−␻k⬘兲t具k兩␮

ˆ 兩k⬘典 · ␧共t兲. 共11兲
dt
⬘
k =0
Ĥ共t兲 = Ĥ␲ − ␮
ˆ · ␧共t兲, 共6兲
The coupled equations can be numerically solved by using a
where ␮ˆ is the electric dipole moment operator. In this semi- conventional algorithm, e.g., Runge-Kutta method.
empirical model, ␮ ˆ is expanded in terms of 兵n̂m␴其 as
ˆ = − e 兺 Rmn̂m␴ .
␮ 共7兲
m,␴ C. „Angular… momentum operator and its approximate
eigenstates
Equation 共7兲 implies that a ␲ electron occupying 兩␹m典 is as-
sumed to be localized just at the nuclear coordinate Rm. The In this semiempirical model, ␲-electron rotation can be
time-dependent Schrödinger equation 共TDSE兲 for a quantified by the momentum expectation value p共t兲
␲-electron wave packet is ⬅ 具⌿共t兲兩p̂兩⌿共t兲典, where p̂ is defined using the momentum of
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 204314-4 Kanno et al.
complex MOs for a circular path along an aromatic ring.
Complex MOs 兵兩␺ j典其 of an aromatic molecule of DMh sym-
metry are given by
冉 冊
M
1 2j␲
兩␺ j典 = 1/2 兺 exp i m 兩␹m典,
M m=1 M
where M denotes the number of atoms in the aromatic ring,
e.g., M = 6 for benzene. The integer j reads j = −M / 2
+ 1 , . . . , 0 , . . . , M / 2. 兩␺0典 and 兩␺ M/2典 are the lowest and high-
est orbitals in energy, respectively, and for the other values of
j, 兩␺ j典 and 兩␺−j典 are degenerate.15 By approximating a po-
lygonal structure of the molecule with a complete cylindrical
ring, the complex MO 兩␺ j典 can be regarded as a traveling
wave with the momentum p j for a circular path along the
ring,16
再 冎
jប/b 共1 艋 兩j兩 艋 M/2 − 1兲
pj =
0 共j = 0,M/2兲,
where b is the radius of the ring. In the case of a six-
membered ring, b is equal to the unit bond length d. The
momentum operator p̂ is defined as
p̂ = 兺 p j␯ˆ j␴ ,
j,␴
where ␯ˆ j␴ is an occupation-number operator of ␲ electrons in
兩␺ j典 with a spin ␴. The expectation value p共t兲 is then calcu-
lated by additions and multiplications of LCAO coefficients,
CI coefficients, phase factors 兵e−i␻kt其, and expansion coeffi-
cients 兵ck共t兲其.
␲ electrons with a nonzero value of p j circulate around
the ring with radius b. Hence, angular momentum of ␲ elec-
trons in 兩␺ j典 is simply given by ᐉ j = bp j, and the angular
momentum operator is expressed as ᐉ̂ = bp̂.
Here, in a circular motion of a particle, angular velocity
of the particle is equivalent to its linear velocity divided by
the radius of the circle. Thus, we also define the rotational
angle of ␲ electrons ␪共t兲 as
冕 t
1
␪共t兲 ⬅ d␶ p共␶兲.
m eb 0
Integration with respect to ␶ in Eq. 共15兲 is implemented nu-
merically using Simpson’s rule. The expectation values p共t兲
and ␪共t兲 are utilized as measures of ␲-electron rotation.
As mentioned above, benzene has a pair of degenerate
␲-electronic excited states with angular momentum ᐉ±1. On
the other hand, DCP has a pair of quasidegenerate
␲-electronic excited states, 兩9典 = 兩5 1Bu典 and 兩10典 = 兩6 1Bu典,
with the energy gap 2ប⌬␻ ⬅ ប共␻10 − ␻9兲 = 0.105 eV 共Table
II兲. The transition dipole moments 具9兩␮ ˆ 兩0典 and 具10兩␮ˆ 兩0典 of
an R enantiomer of DCP are illustrated in Fig. 1, and those of
an S enantiomer are their mirror images. The magnitudes of
具9兩␮ˆ 兩0典 and 具10兩␮
ˆ 兩0典 are 2.02ea0 and 1.63ea0, respectively.
Linear combinations of 兩9典 and 兩10典 give the approximate
eigenstates of ᐉ̂, denoted as 兩⫹典 and 兩⫺典, where 具±兩ᐉ̂兩 ± 典
= ± 0.862ប. For an R enantiomer,
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J. Chem. Phys. 127, 204314 共2007兲
兩 ± 典 = 2−1/2共兩9典 ± i兩10典兲, 共16兲
and for an S enantiomer, the sign ⫾ on the right-hand side of
Eq. 共16兲 is replaced by ⫿. ␲ electrons with positive 共nega-
tive兲 angular momentum travel counterclockwise 共clockwise兲
共12兲 around the ring in Fig. 1.
D. Optimal control of unidirectional ␲-electron
rotation
Achievement of a large 共angular兲 momentum expecta-
tion value requires a linearly polarized laser pulse ␧共t兲 to
transfer as much of the population as possible from the
ground state 兩0典 to either 兩⫹典 or 兩⫺典. In our previous study,5
we designed a single-color linearly polarized laser pulse on
the basis of a three-level 共兩0典, 兩9典, and 兩10典兲 model analysis.
The central frequency of the laser pulse is resonant with the
average energy of the quasidegenerate states. The polariza-
tion unit vector e+ or e− is defined as 具9兩␮ ˆ 兩0典 · e±
共13兲
= ± 具10兩␮ˆ 兩0典 · e± for each enantiomer. The directions of e± for
an R enantiomer are illustrated in Fig. 1. The ultrashort
single-peaked laser pulse applied along e± creates a superpo-
sition 兩9典 ± 兩10典 in 兩⌿共t兲典. Then, the relative phase between 兩9典
and 兩10典 temporally evolves as ±1 → ⫿ i → ⫿ 1 → ± i → ± 1
→ . . . with the progression of time after excitation, 0 → T / 4
共14兲 → T / 2 → 3T / 4 → T → . . ., where T ⬅ ␲ / ⌬␻. In T / 4 and 3T / 4
after excitation, ␲ electrons circulate around the ring of DCP
in the direction specified by the relative phase at the moment.
In this study, we designed a linearly polarized laser pulse
using the OCT. In the OCT, a positive definite operator Ô,
which takes a maximum expectation value when the system
reaches a target state, is introduced. The optimal control
pulse ␧共t兲 is designed so as to maximize the expectation
value of Ô at the final time t f subject to minimum laser
energy. That is, ␧共t兲 is defined as the laser pulse that gives a
maximum value to the objective functional,
J = 具⌿共t f 兲兩Ô兩⌿共t f 兲典 −
1
បA
冕 0
tf
dt关␧共t兲兴2
冋 册
− 2 Re 冕 tf
dt具⌳共t兲兩
⳵ 1
− Ĥ共t兲 兩⌿共t兲典,
⳵t iប
共17兲
0
共15兲 where A is a positive parameter to weigh the penalty for laser
energy and 兩⌳共t兲典 is a Lagrange multiplier for 兩⌿共t兲典 to sat-
isfy the TDSE. According to the variational procedure, the
requirement of ␦J = 0 gives the equation that 兩⌳共t兲典 satisfies,
⳵
iប 兩⌳共t兲典 = Ĥ共t兲兩⌳共t兲典, 共18兲
⳵t
with the final condition
兩⌳共t f 兲典 = Ô兩⌿共t f 兲典. 共19兲
The explicit form of the optimal control pulse ␧共t兲 is even-
tually derived as
␧共t兲 = − A Im关具⌳共t兲兩␮
ˆ 兩⌿共t兲典 · eopt兴eopt , 共20兲
where eopt is the polarization unit vector of ␧共t兲.
The coupled Eqs. 共8兲, 共18兲, and 共20兲 need to be solved
simultaneously by means of an iteration algorithm.6 Starting
 204314-5 Ring currents in chiral aromatic molecules J. Chem. Phys. 127, 204314 共2007兲

with the initial condition 共9兲, we perform time propagation of

兩⌿共t兲典 forward by numerically integrating Eq. 共11兲 with an
initial trial pulse. Then, Lagrange multiplier 共19兲 at t = t f is
set using the ␲-electron wave packet at t = t f , and backward
time propagation of 兩⌳共t兲典 is implemented; 兩⌳共t兲典 is ex-
panded in terms of 兵兩k典其, and the counterpart of Eq. 共11兲 for
兩⌳共t兲典 is solved. Forward time propagation of 兩⌿共t兲典 is sub-
sequently carried out. The laser pulse ␧共t兲 is calculated from
Eq. 共20兲 in both the backward and forward time propaga-
tions. This iteration step is repeated until convergence is
achieved. The laser pulse finally obtained is regarded as an
optimal control pulse.

III. RESULTS AND DISCUSSION

We here present the results of optimal control simula-

tions within 17-state expansion for counterclockwise and
clockwise ␲-electron rotations in an R enantiomer of DCP.
The positive definite operator Ô is determined for each
␲-electron rotation. For counterclockwise ␲-electron rota-
tion, the target state, which needs to have a maximum value
of the population at the final time t f , is 兩⫹典. Therefore, Ô is
set simply as the projection operator onto 兩⫹典,

Ô = 兩 + 典具+ 兩. 共21兲
In the same manner, for clockwise ␲-electron rotation, we
have

Ô = 兩− 典具− 兩. 共22兲
The control time 共pulse duration兲 is chosen to be equal to one
oscillation cycle corresponding to the energy gap between 兩9典
and 兩10典: t f = T = 39.5 fs. In numerical applications, the pen-
alty parameter A should be set to an appropriate value.
Throughout this article, we adopt A = 5.0⫻ 10−3Eh / 共ea0兲2. In
all calculations below, convergence is assumed when ⌬J, the
difference in J between the last two iteration steps, satisfies
⌬J / J ⬍ 10−6.
To examine the polarization-direction dependence of the
efficiency of laser-induced ␲-electron rotation, we varied the
angle of the polarization vector eopt. Hereafter, ␾k 共k = opt, ⫹,
and ⫺兲 signify the angles of ek from the x axis in Fig. 1. For
counterclockwise 共clockwise兲 ␲-electron rotation, ␾opt was
varied with an interval of ±10° from ␾−共␾+兲: ␾opt − ␾−共␾+兲
= 0 ° , ± 10° , ± 20° , . . . , ± 90°. The initial trial pulse at ␾opt
− ␾−共␾+兲 = 0° was the so-called ␲ pulse.17 Then, the initial
trial pulse at ␾opt − ␾−共␾+兲 = ± ⌽ was the optimal control
pulse ␧共t兲 at ␾opt − ␾−共␾+兲 = ± 共⌽ − 10° 兲, where ⌽
= 10° , 20° , . . . , 90°.
Figure 2共a兲 shows the results of optimal control simula-
tions for counterclockwise ␲-electron rotation. Here, objec-
tive functional J and target yield P+共t f 兲 ⬅ 兩具+兩⌿共t f 兲典兩2 that
corresponds to the first term in Eq. 共17兲 具⌿共t f 兲兩Ô兩⌿共t f 兲典 are
plotted as a function of angle shift ␾opt − ␾−. The objective
functional J and the target yield P+共t f 兲 at each angle shift are
denoted by circles and squares, respectively. In Fig. 2共a兲,
both J and P+共t f 兲 exhibit two maxima at ␾opt − ␾− = 0° 共eopt
= e−兲 and −80° 共eopt ⯝ e+兲 as well as two minima at ␾opt
− ␾− = −40° 共具9兩␮ ˆ 兩0典 · eopt ⯝ 0兲 and 50° 共具10兩␮ ˆ 兩0典 · eopt ⯝ 0兲.
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FIG. 2. 共a兲 Objective functional J and target yield P+共t f 兲 ⬅ 兩具+兩⌿共t f 兲典兩2 for
counterclockwise ␲-electron rotation as a function of angle shift ␾opt − ␾−.
The objective functional J and the target yield P+共t f 兲 at each angle shift are
denoted by circles and squares, respectively. 共b兲 Objective functional J and
target yield P−共t f 兲 ⬅ 兩具−兩⌿共t f 兲典兩2 for clockwise ␲-electron rotation as a func-
tion of angle shift ␾opt − ␾+. The objective functional J and the target yield
P−共t f 兲 at each angle shift are denoted by circles and squares, respectively.
The maxima have almost the same values of J or P+共t f 兲 and
the minima as well. The similar tendencies in J and P+共t f 兲
indicate that the laser energy of the optimal control pulse
␧共t兲, i.e., the second term in Eq. 共17兲, is almost uniform over
the whole range of angle shift ␾opt − ␾−. Figure 2共b兲 shows
objective functional J and target yield P−共t f 兲 ⬅ 兩具−兩⌿共t f 兲典兩2
for clockwise ␲-electron rotation as a function of angle shift
␾opt − ␾+. In analogy with the case of Fig. 2共a兲, both J and
P−共t f 兲 in Fig. 2共b兲 show two maxima at ␾opt − ␾+ = 0° 共eopt
= e+兲 and 80° 共eopt ⯝ e−兲 as well as two minima at ␾opt − ␾+
= −50° 共具10兩␮ ˆ 兩0典 · eopt ⯝ 0兲 and 40° 共具9兩␮ ˆ 兩0典 · eopt ⯝ 0兲. The
other features in Fig. 2共a兲 such as uniformity of laser energy
are also found in Fig. 2共b兲.
The fact that the minima of objective functional or target
yield appear at 具9兩␮ ˆ 兩0典 · eopt ⯝ 0 and 具10兩␮
ˆ 兩0典 · eopt ⯝ 0 is intu-
itively understandable. When eopt is orthogonal to 具9兩␮ ˆ 兩0典
共具10兩␮ ˆ 兩0典兲 and the mixing of excited states other than the
three key levels 兩0典, 兩9典, and 兩10典 into 兩⌿共t兲典 is negligibly
small, the ground state 兩0典 is coupled only to 兩10典 共兩9典兲. At
most, only half of the population can be transferred to the
 204314-6 Kanno et al. J. Chem. Phys. 127, 204314 共2007兲

target state, as in Figs. 2共a兲 and 2共b兲, but at the same time,
the other approximate angular momentum eigenstate is
equally populated. No ␲-electron rotation is induced. To
verify this, we have performed optimal control simulations
for counterclockwise and clockwise ␲-electron rotations ex-
actly at 具9兩␮ ˆ 兩0典 · eopt = 0 and 具10兩␮ ˆ 兩0典 · eopt = 0. The initial trial
pulse at 具9兩␮ ˆ 兩0典 · eopt = 0 共具10兩␮ ˆ 兩0典 · eopt = 0兲 was the optimal
control pulse ␧共t兲 at 具9兩␮ ˆ 兩0典 · eopt ⯝ 0 共具10兩␮ ˆ 兩0典 · eopt ⯝ 0兲
mentioned above. For both ␲-electron rotations, we have
confirmed that the optimal control pulse ␧共t兲 at
具9兩␮ˆ 兩0典 · eopt = 0 共具10兩␮ ˆ 兩0典 · eopt = 0兲 is a cosine wave with fre-
quency ␻10 共␻9兲 and, thus, coherent excitation 兩0典 → 兩10典
共兩9典兲 takes place. Calculated momentum expectation value
p共t兲 and rotational angle ␪共t兲 are almost 0 throughout the
control.
On the other hand, what causes the maxima at eopt = e−
and e+? If the optimal control pulse ␧共t兲 at these angle shifts
is an ultrashort single-peaked laser pulse, appearance of the
maxima could be explained. As stated in Sec. II D, an ul-
trashort single-peaked laser pulse with e−共e+兲 produces 兩⫹典
in an R enantiomer in T / 4共3T / 4兲 after excitation. Hence, in
principle, it is possible to create a large amount of population
in 兩⫹典 at t = t f by setting the pulse peak of an ultrashort
single-peaked laser pulse with e−共e+兲 prior to the final time t f
by T / 4共3T / 4兲. Likewise, the final population of 兩⫺典 can be
enriched by applying an ultrashort single-peaked laser pulse
with e+共e−兲 so that its pulse peak is at t = t f − T / 4共3T / 4兲.
Here, a simple but important question arises: Is the optimal FIG. 3. 共a兲 Optimal control pulse ␧共t兲 at ␾opt − ␾− = 0° 共eopt = e−兲 for coun-
terclockwise ␲-electron rotation. Inset: Power spectrum of the optimal con-
control pulse ␧共t兲 at eopt = e− or e+ indeed an ultrashort trol pulse ␧共t兲, S共␻兲, defined by Eq. 共23兲. The values of S共␻兲 are scaled so
single-peaked laser pulse? that the maximum value is unity. 共b兲 Temporal behavior in the populations
Temporal behavior in the optimal control pulse ␧共t兲 at of 兩0典 共dotted line兲, 兩⫹典 共solid line兲, and 兩⫺典 共dash-dotted line兲 denoted as
␾opt − ␾− = 0° 共eopt = e−兲 for counterclockwise ␲-electron rota- P0共t兲, P+共t兲, and P−共t兲, respectively. 共c兲 Expectation value of momentum
p共t兲. 共d兲 Expectation value of rotational angle ␪共t兲.
tion is shown in Fig. 3共a兲. The wave profile of the optimal
control pulse ␧共t兲 in Fig. 3共a兲 is completely different from
that of an ultrashort single-peaked laser pulse. It rather re- ␧共t兲 ⯝ ␧ cos共⌬␻t + ␸env兲cos关共␻9 + ⌬␻兲t + ␸osc兴eopt , 共25兲
sembles that of a wave with a trigonometric envelope. The
envelope starts with a nonzero value and reaches zero at t where ␸env ⬅ 共␸10 − ␸9兲 / 2 and ␸osc ⬅ 共␸9 + ␸10兲 / 2. Now, ␧共t兲
= 11 fs. The peak of the envelope is located at t = 31 fs. The is characterized by the three parameters ␧, ␸env, and ␸osc.
inset of Fig. 3共a兲 shows the power spectrum of ␧共t兲, S共␻兲, Equation 共25兲 consists of two parts: a slowly oscillating part
defined as the absolute square of the Fourier transform of ␧ cos共⌬␻t + ␸env兲 with amplitude ␧, frequency ⌬␻, and phase
␧共t兲, ␸env, which works as an envelope of ␧共t兲, and a rapidly os-
cillating part cos关共␻9 + ⌬␻兲t + ␸osc兴, resonant with the aver-

S共␻兲 ⬅ 冏冕 ⬁

−⬁
dt␧共t兲e−i␻t 冏 2
. 共23兲
The values of S共␻兲 in the inset are scaled so that the maxi-
mum value is unity. The power spectrum S共␻兲 shows two
main peaks with the same intensity at around ប␻ = 7.66 and
7.77 eV that are equal to ប␻9 and ប␻10, respectively. There-
fore, the optimal control pulse ␧共t兲 in Fig. 3共a兲 can be ap-
proximated by a linear combination of cosine waves with
frequencies ␻9 and ␻10,
␧共t兲 ⯝ 关␧9 cos共␻9t + ␸9兲 + ␧10 cos共␻10t + ␸10兲兴eopt , 共24兲
where ␧k and ␸k 共k = 9 and 10兲 are the amplitude and phase of
the wave with frequency ␻k, respectively. When ␧9 = ␧10
⬅ ␧ / 2, Eq. 共24兲 can be rewritten as
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age energy of the quasidegenerate states 兩9典 and 兩10典. Among
the three parameters, ␧ and ␸env that specify the envelope of
␧共t兲 are especially important. For ␧共t兲 in Fig. 3共a兲, we esti-
mate that ␧ is 0.98 GV m−1 and ␸env is 0.22␲ rad.
Figure 3共b兲 shows the temporal behavior in the popula-
tions of 兩0典, 兩⫹典, and 兩⫺典 denoted by dotted, solid, and dash-
dotted lines, respectively. We use the notations Pk共t兲
⬅ 兩具k 兩 ⌿共t兲典兩2 共k = 0, ⫹, and ⫺兲 for those populations.
Throughout the control, the sum of P0共t兲, P+共t兲, and P−共t兲 is
almost unity; that is, the system behaves similar to a three-
level system. Momentum expectation value p共t兲 and rota-
tional angle ␪共t兲 are plotted in Figs. 3共c兲 and 3共d兲, respec-
tively. At t ⬍ 13 fs, a small amount of the population is
excited from the ground state 兩0典 and P+共t兲 exceeds P−共t兲
关Fig. 3共b兲兴. Accordingly, ␲ electrons start to rotate counter-
clockwise around the ring in Fig. 1 关Fig. 3共c兲兴. After that, the
population created in 兩⫹典 completely shifts to 兩⫺典 and the
 204314-7 Ring currents in chiral aromatic molecules
FIG. 4. 共a兲 Optimal control pulse ␧共t兲 at ␾opt − ␾− = −77.6° 共eopt = e+兲 for
counterclockwise ␲-electron rotation. Inset: Power spectrum of the optimal
control pulse ␧共t兲, S共␻兲, defined by Eq. 共23兲. The values of S共␻兲 are scaled
so that the maximum value is unity. 共b兲 Temporal behavior in the popula-
tions of 兩0典 共dotted line兲, 兩⫹典 共solid line兲, and 兩⫺典 共dash-dotted line兲 denoted
as P0共t兲, P+共t兲, and P−共t兲, respectively. 共c兲 Expectation value of momentum
p共t兲. 共d兲 Expectation value of rotational angle ␪共t兲.
rotation direction of ␲ electrons is reversed. The value of
␪共t兲 increases to 0.6⫻ 2␲ rad and then decreases back to 0
关Fig. 3共d兲兴. At t ⬎ 25 fs, the optimal control pulse ␧共t兲 ap-
proaches and then passes its peak intensity. The population
remaining in 兩0典 is drastically pumped up and that in 兩⫺典 also
moves to 兩⫹典. In parallel, P+共t兲 exhibits a sharp rise and
finally, the target yield P+共t f 兲 is 0.94. The momentum of ␲
electrons at the final time t f reaches p共t f 兲 = 0.305ប / a0 共corre-
sponding to 0.806ប of angular momentum兲, and ␲ electrons
are estimated to circulate counterclockwise around the ring
more than four times within this control time.
We have carried out an optimal control simulation for
counterclockwise ␲-electron rotation at ␾opt − ␾− = −77.6°
共exactly eopt = e+兲. The initial trial pulse was the optimal con-
trol pulse ␧共t兲 at ␾opt − ␾− = −80° 共eopt ⯝ e+兲. Figure 4共a兲
shows the temporal behavior in the optimal control pulse
␧共t兲. The peak and zero point of a trigonometric envelope of
␧共t兲 are found at t = 10 and 30 fs, respectively. The power
spectrum S共␻兲 is displayed in the inset. The values of S共␻兲 in
the inset are scaled so that the maximum value is unity. As in
the case of Fig. 3共a兲, two main peaks of S共␻兲 are observed
with the same intensity at around ប␻ = ប␻9 and ប␻10. Thus,
the optimal control pulse ␧共t兲 in Fig. 4共a兲 can also be ap-
proximated by Eq. 共24兲 or 共25兲. Here, we estimate that ␧ is
0.90 GV m−1 and ␸env is −0.26␲ rad. The ratio of ␧ in the
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J. Chem. Phys. 127, 204314 共2007兲
cases of Figs. 3共a兲 and 4共a兲, i.e., ␧共eopt = e−兲 / ␧共eopt = e+兲, is
equal to 兩具k兩␮ ˆ 兩0典 · e+ / 具k兩␮
ˆ 兩0典 · e−兩 共k = 9 and 10兲, and Rabi fre-
quencies ⍀k ⬅ −具k兩␮ ˆ 兩0典 · ␧eopt / 2ប in the two cases, therefore,
have the same magnitude. The phase ␸env is responsible for
the timings of the peak and zero point of the envelope of
␧共t兲. Since the value of ␸env for eopt = e+ differs from that for
eopt = e− by almost ␲ / 2 rad, the order of the peak and zero
point in Fig. 4共a兲 is reversed from that in Fig. 3共a兲.
The dotted, solid, and dash-dotted lines in Fig. 4共b兲 de-
note the temporal behavior in P0共t兲, P+共t兲, and P−共t兲, respec-
tively. Momentum expectation value p共t兲 and rotational
angle ␪共t兲 are plotted in Figs. 4共c兲 and 4共d兲, respectively. The
populations Pk共t兲 共k = 0, ⫹, and ⫺兲 change quite differently
in time from those in Fig. 3共b兲. In Fig. 4共b兲, a considerable
amount of the population is transferred from 兩0典 after the
optimal control pulse ␧共t兲 is turned on. The population trans-
fer continues until t = 21 fs and almost all of the population
pumped from 兩0典 is brought to 兩⫺典, whereas the approximate
angular momentum eigenstate first populated in Fig. 3共b兲 is
兩⫹典. ␲ electrons travel clockwise at about t = 21 fs 关Fig.
4共c兲兴. Subsequently, the population in 兩⫺典 starts to shift to
兩⫹典 and P+共t兲 is rapidly increased. When P+共t兲 overtakes
P−共t兲 at t = 30 fs, the sign of p共t兲 is changed from minus to
plus, and the value of ␪共t兲 begins to increase just after reach-
ing −8.76⫻ 2␲ rad. Eventually, at t = t f , the target yield
P+共t f 兲 is 0.95, while 兩⫺典 is emptied. 共Angular兲 momentum of
␲ electrons at the final time t f is as large as that in Fig. 3共c兲,
though the rotational angle still has a negative value
共−4.35⫻ 2␲ rad兲.
The optimal control pulse ␧共t兲 at eopt = e+ 共e−兲 for clock-
wise ␲-electron rotation is very similar to that at eopt = e− 共e+兲
for counterclockwise ␲-electron rotation. They have almost
the same values of ␧ and ␸env since 兩具k兩␮ ˆ 兩0典 · e+ / 具k兩␮
ˆ 兩0典 · e−兩
⯝ 1 共k = 9 and 10兲. Temporal behavior in Pk共t兲 共k = 0, ⫹, and
⫺兲 at eopt = e+ 共e−兲 for clockwise ␲-electron rotation is also
analogous to that at eopt = e− 共e+兲 for counterclockwise
␲-electron rotation except that the solid and dash-dotted
lines in Fig. 3共b兲 关Fig. 4共b兲兴 are switched to signify P−共t兲 and
P+共t兲, respectively. Hence, the values of p共t兲 and ␪共t兲 at
eopt = e+ 共e−兲 for clockwise ␲-electron rotation are given just
by inverting their signs in Figs. 3共c兲 and 3共d兲 关Figs. 4共c兲 and
4共d兲兴, respectively.
In this article, we used a restricted basis set of 17
␲-electronic states to expand 兩⌿共t兲典 out of 136 singlet eigen-
states of Ĥ␲ obtained by SDCI. Klamroth et al. pointed out
that the use of a restricted basis set may result in misestima-
tion of laser-driven coupled electron-nuclear dynamics of a
molecule-surface system.18 In addition to the 17 ␲-electronic
states, our PPP calculation revealed a few highly excited 1Ag
states of which energies are almost twice as large as that of
兩9典 or 兩10典. If those 1Ag states are included in the expansion
of 兩⌿共t兲典, a linearly polarized laser pulse in Fig. 3共a兲 关Fig.
4共a兲兴 applied along e−共e+兲 will populate them by two-photon
excitations. As a result, target yield P+共t f 兲 decreases by less
than 0.1 and momentum expectation value p共t兲 is accord-
ingly reduced. Thus, the inclusion of highly excited 1Ag
states does not semiquantitatively affect our findings.
As clearly shown in Figs. 3 and 4, the phase of the
 204314-8 Kanno et al.
envelope of ␧共t兲, ␸env, is a crucial parameter for determina-
tion of the rotation direction of ␲ electrons. By setting a
proper value of ␸env, ␲ electrons can be rotated in an in-
tended direction at the final time t f regardless of whether
eopt = e− or e+. In contrast, ␲-electron rotation is highly insen-
sitive to the phase of the rapidly oscillating part of ␧共t兲, ␸osc.
Numerical simulations assuming a linearly polarized laser
field expressed by Eq. 共25兲 with ␸osc = ± ␲ / 2 rad, with which
the laser field starts at zero, provide almost the same results
as those obtained from optimal control simulations.
␲-electron rotation can be controlled efficiently by applying
a two-color laser field with its phases properly tuned, while
the timing of a pulse peak is utilized to control the rotation
direction for conventional excitation with an ultrashort
single-peaked laser pulse.
Each of the polarization vectors e− and e+ has its “pre-
ferred” rotation direction: Counterclockwise for e− and
clockwise for e+. After a linearly polarized laser field is
turned on, ␲ electrons start to rotate in the preferred rotation
direction defined by the polarization vector, regardless of
whether the laser field is a two-color laser field or an ul-
trashort single-peaked laser pulse. Then, population transfer
occurs between 兩⫹典 and 兩⫺典 and, therefore, 共angular兲 mo-
mentum of ␲ electrons oscillates between positive and nega-
tive values. Finally, ␲ electrons circulate in the rotation di-
rection specified by the target state with a large amount of
共angular兲 momentum at the end of the control. The difference
between the two cases is that the sum of P+共t兲 and P−共t兲
increases during control by a two-color laser field but does
not change throughout population oscillation between 兩⫹典
and 兩⫺典 for excitation with an ultrashort single-peaked laser
pulse.
Objective functional J and target yield P+共t f 兲 关P−共t f 兲兴 at
eopt = e+ 共e−兲 for counterclockwise 共clockwise兲 ␲-electron ro-
tation are as high as those at eopt = e− 共e+兲, but they depend on
control time. If control time is short, e.g., t f = 25 fs, less
population is excited from the ground state 兩0典 at eopt = e+
共e−兲, of which preferred rotation direction does not coincide
with the rotation direction specified by the target state, than
at eopt = e− 共e+兲. Consequently, with a short control time, J
and P+共t f 兲 关P−共t f 兲兴 at eopt = e+ 共e−兲 are lower than those at
eopt = e− 共e+兲. This finding is also true for control by an ul-
trashort single-peaked laser pulse; with control time shorter
than 3T / 4, the population created in 兩⫺典 cannot fully shift to
兩⫹典 at the final time t f .
IV. CONCLUSIONS AND PROSPECTS
In conclusion, we have carried out optimal control simu-
lations of ␲-electron rotation 共ring current兲 in a six-
membered chiral aromatic molecule, DCP, assuming a linear
polarization. First, the field-free ␲-electronic structure of
DCP was evaluated within a framework of semiempirical
molecular orbital theory. Next, the optimal control pulse ␧共t兲
was designed using the global optimal control theory. Nu-
merical simulations were performed in an R enantiomer for
counterclockwise and clockwise ␲-electron rotations. In or-
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J. Chem. Phys. 127, 204314 共2007兲
der to investigate the polarization-direction dependence of
the efficiency of ␲-electron rotation, the angle of the polar-
ization vector eopt was varied.
For both counterclockwise and clockwise ␲-electron ro-
tations, the calculated objective functional J and target yield
P+共t f 兲 关P−共t f 兲兴 show two maxima at eopt = e− and eopt = e+ as
well as two minima at 具9兩␮ ˆ 兩0典 · eopt = 0 and 具10兩␮
ˆ 兩0典 · eopt = 0.
The maxima have almost the same value of J or P+共t f 兲
关P−共t f 兲兴 and the minima as well. The origin of the minima is
that the ground state 兩0典 is coupled to only one of 兩9典 and
兩10典. The optimal control pulse ␧共t兲 at eopt = e− or e+ consists
of a two-color laser field with frequencies ␻9 and ␻10 in
which the two frequency components have the same inten-
sity. The phase of the envelope of ␧共t兲, ␸env, is a crucial
parameter for determination of the rotation direction of ␲
electrons. In our previous study,5 the rotation direction was
controlled by adjusting the timing of the pulse peak of an
ultrashort single-color linearly polarized laser pulse. In con-
trast, in the present study, the rotation direction was effi-
ciently controlled by tuning the phase of each frequency
component of a two-color laser field.
The present optimal control pulses are individualized by
a sudden switch on and switch off, which are difficult for
experimental application. This can be solved by replacing a
constant parameter A in the laser-energy term of the objec-
tive functional J with a time-dependent penalty function
A共t兲.7,8 By making it a smooth function starting and ending at
zero, the envelope of the optimal control pulse ␧共t兲 shows
adiabatic ramp and decay.
In this article, we neglected nuclear degrees of freedom
since the period of ␲-electron rotation is significantly shorter
than the vibration periods of nuclei with the control time of
39.5 fs. Effects of nuclear motions on ␲-electron dynamics
need to be taken into account when the duration of
␲-electron rotation is close to vibration periods. In this case,
the Born-Oppenheimer approximation breaks down and the
quasidegenerate states 兩9典 and 兩10典 couple to each other
through nuclear vibrations. Our next step is to consider ef-
fects of nuclear motions on ␲-electron rotation by propagat-
ing the total wave function composed of both nuclear and
␲-electron wave packets.
The optimal control theory is promising for application
to laser detection of molecular chirality, for example, for
designing the optimal control pulse ␧共t兲 that maximizes the
target yield P+共t f 兲 or P−共t f 兲 in an R enantiomer and mini-
mizes the counterpart in an S enantiomer simultaneously
with a given penalty parameter. ␲-electron rotation con-
trolled by the optimal control pulse ␧共t兲 may be experimen-
tally detected using attosecond time-resolved photoelectron
spectroscopy.19,20
ACKNOWLEDGMENTS
M.K. is grateful to Dr. Y. Teranishi, Professor T. Kato,
and Professor Y. Ohtsuki for valuable discussions and ac-
knowledges financial support from a JSPS Research Fellow-
ship for Young Scientists 共No. 18·5252兲. This work was
partly supported by a JSPS Research Grant 共No. 17350004兲.
 204314-9 Ring currents in chiral aromatic molecules J. Chem. Phys. 127, 204314 共2007兲

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