Chemical Physics 379 (2011) 13–22

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Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Free-time and fixed end-point multi-target optimal control theory:

Application to quantum computing
K. Mishima ⇑, K. Yamashita
Department of Chemical System Engineering, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi-shi, Saitama 332-0012, Japan

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

Article history: An extension of free-time and fixed end-point optimal control theory (FRFP-OCT) to monotonically con-
Received 21 May 2010 vergent free-time and fixed end-point multi-target optimal control theory (FRFP-MTOCT) is presented.
In final form 2 October 2010 The features of our theory include optimization of the external time-dependent perturbations with high
Available online 27 October 2010
transition probabilities, that of the temporal duration, the monotonic convergence, and the ability to opti-
mize multiple-laser pulses simultaneously. The advantage of the theory and a comparison with conven-
Keywords: tional fixed-time and fixed end-point multi-target optimal control theory (FIFP-MTOCT) are presented by
Free-time and fixed end-point multi-target
comparing data calculated using the present theory with those published previously [K. Mishima,
optimal control theory
Rotational modes of molecules
K. Yamashita, Chem. Phys. 361, (2009), 106]. The qubit system of our interest consists of two polar NaCl
Quantum computing molecules coupled by dipole–dipole interaction. The calculation examples show that our theory is useful
Deutsch-Jozsa algorithm for minor adjustment of the external fields.
Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, quantum computing and entanglement genera-
tion using molecular internal degrees of freedom (electronic, vibra-
tional and rotational modes) have been studied extensively, both
theoretically and numerically [1–22]. The essential task of quan-
tum computing is to drive a given initial state to the desired target
state by means of external perturbations. In most cases, the exter-
nal perturbations used to control molecular states are laser fields,
magnetic fields, etc. depending on the molecular mode of interest.
Several theoretical approaches for performing the task have
been proposed so far. If we limit ourselves to quantum computing,
multi-target optimal control theory (MTOCT) [2,7,23], adiabatic
rapid passage (ARP) [24,25], stimulated Raman adiabatic passage
(STIRAP) [26–29] and so on have been the basic methods for quan-
tum computing. Of course, these techniques originally stemmed
from the necessity of controlling physical and chemical quantum
dynamics. It is plain that there is a close relationship between
quantum control and quantum computing because quantum com-
puting is a sequence of unitary transformations of two-level sys-
tems, which can be viewed as a sequence of chemical reactions.
Therefore, it is also important to construct some new methods
beyond the conventional control methods to control quantum
dynamics efficiently.
⇑ Corresponding author at: Department of Chemical System Engineering, Graduate
School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan.
E-mail address: erdao@tcl.t.u-tokyo.ac.jp (K. Mishima).
Although all the above-mentioned methods are used for quan-
tum computing, the most ubiquitous and popular one is MTOCT.
In our opinion, MTOCT will remain the best theoretical method to
tailor gate laser pulses and will continue to be improved in connec-
tion with quantum computing in the future, especially for molecu-
lar quantum computing. The reason is that one of the requirements
of quantum computing is to process a given quantum unitary gate
for any inputs that MTOCT can process. It would be difficult to do
this if the other methods mentioned above were employed in
realistic molecular systems that consist of a number of eigenstates.
In our previous works [30,31], we found that entanglement gene-
ration in general quantum systems crucially relies on the strength
of entangling interactions among distinct quantum systems. We
stressed that if the entangling interactions are strong, the maxi-
mally entangled state can be created in a short time. This in turn
implies that if the entangling interactions are weak, laser fields
should be long enough. Concretely speaking, the temporal duration
of the laser pulses by which the maximally entangled states can be
created is inversely proportional to the strength of the entangling
interaction. This work prompted further work [32,33], where
free-time and fixed end-point optimal control theories (FRFP-
OCTs) were proposed for the control of non-dissipative and dissi-
pative quantum systems. The features of these theories lie in the
correct determination of the temporal duration of the external per-
turbations, transition probabilities higher than those calculated
using fixed-time and fixed end-point optimal control theories
(FIFP-OCT), and absence of the penalty factor. It should again be
emphasized that the optimal time duration of the external

0301-0104/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemphys.2010.10.003
14 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22

perturbations is not known exactly in advance in most cases. On MTOCT has been proposed and applied to a number of quantum
the other hand, in [12], we found that the gate fidelities and cor- control problems, especially in connection with quantum comput-
rectness of the measurement results of the Deutsch–Jozsa algo- ing. However, conventional MTOCT treats only fixed-time and fixed
rithm were best when the rotational modes of dipole–dipole end-point optimal control problems.
coupled molecules were used as qubit systems in comparison with First, we present the details of the derivation of FRTP-MTOCT.
any combinations of intramolecular degrees of freedom reported As in our previous work [32,33], we introduce real-time t and ficti-
so far. This result seems to be due to weak intensities of control tious-time s, which are related by the following equality:
and target laser pulses and because the adjacent level spacing in- t ¼ TðsÞs; ð3Þ
creases with increasing rotational quantum number, leading us where s ranges from zero to unity and is dimensionless. In addition,
to regard the rotational mode of molecules as ‘‘qubit” rather than we have included the implicit dependence of T on the dimension-
‘‘qudit” although the rotational state of molecules is essentially less parameter s in Eq. (3). As shown below, Eq. (3) removes the
multi-level, i.e., qudit. Note that in [12] also we extended the con- constraint of the final time of the optimized laser pulses. The
ventional MTOCT to multiple-pulse MTOCT. time-dependent equation for jWik(t)i is given by the conventional
From the above statement, the aim of the present work is to ex-
Schrödinger equation:
tend our FRFP-OCTs to free-time and fixed end-point multi-target ( )
@jWik ðtÞi X
N !
optimal control theory (FRFP-MTOCT), especially in light of the fu- ih ¼ b
H ln  E ðtÞ jWik ðtÞi;
~ ð4Þ
ture development of molecular quantum computers. In connection @t n¼1
n

with our work [12], we also take into account in the new theory the where!H b is the 0th order Hamiltonian consisting of N molecules and
case where multiple laser different pulses irradiate different mole-
ln  En ðtÞ is the laser-molecule interaction for the nth molecule.
~
cules individually. We compare the present results with those re- Substituting the relationship of Eq. (3) into Eq. (4), we obtain the
ported in [12], and find that although the correctness of the final
fictitious-time Schrödinger equation for N molecules:
stage of the measurement process of the Deutsch–Jozsa algorithm ( )
@jWik ðsÞi X
N !
is not necessarily better than that obtained in [12], the transition ih ¼ b
H ln  E ðsÞ jWik ðsÞiTðsÞ:
~ ð5Þ
probabilities of each gate are slightly better than those reported @s n¼1
n

in [12]. These numerical results mean that FRFP-MTOCT is better

Usually, the objective functional to be maximized or minimized is
than fixed-time and fixed end-point multi-target optimal control
constrained by some of the factors, e. g., the equation of dynamics
theory (FIFP-MTOCT). Therefore, it is important to generalize our
that the problem in mind follows. In this case, we can add such con-
previous FRFP-OCTs to FRFP-MTOCT.
straints into Eq. (1) using Lagrange multipliers and we obtain the
The present paper is organized as follows. In Section 2, we
new objective functional J:
briefly introduce the theoretical aspects of MTOCT proposed to z h
X 
date and show the detailed derivation of FRFP-MTOCT. In Section J¼ hWik ðs ¼ 1ÞjUfk i2
3, we compare the numerical results calculated using FRFP-MTOCT k¼1
(Z (
* ! ) +
and those calculated using the conventional MTOCT [12], and dis- 1  i XN ! 
 b @ 
cuss the advantage of FRFP-MTOCT, taking the rotational modes of  2Re Wfk ðsÞ H ln  En ðsÞ þ
~ Wik ðsÞ
0  h  TðsÞ@ s 
two dipole–dipole coupled two NaCl molecules as two qubits. Sec- )# Z
n¼1

tion 4 is devoted to concluding remarks and future aspects. For 1

@TðsÞ
notational convenience, the normalization constants of wavefunc- TðsÞds  m T ð sÞ ds: ð6Þ
0 @s
tions are omitted in what follows.
The second term of the right-hand side of Eq. (6) is the requirement
that the Schrödinger equation, Eq. (5), should be satisfied at all
2. Theory and algorithm
times during time evolution. On the other hand, the third term of
the right-hand side of Eq. (6) ensures that the time derivative of
We assume that the quantum system of our interest is sepa-
T(s), @T(s)/@ s, is zero at all times. The Lagrange multipliers for
rated from the surrounding environment so that our system can
jWik(s)i and oT(s)/@ s are given by jWfk(s)i and mT(s), respectively.
be described adequately by the Schrödinger equation. The objec-
The variation of J leads to:
tive functional to be maximized in our problem is given by:
X
z
  
X
z
2 dJ ¼ 2Re hWik ðs ¼ 1ÞjUfk ihUfk jdWik ðs ¼ 1Þi
J¼ jhWik ðTÞjUfk ij ; ð1Þ k¼1
k¼1 Z (*  " # +
i 
 b X~ !
1 N

where jWik(t)i is the kth time-dependent wavefunction at time t and 2 dsRe dWfk ðsÞ H  ln  En ðsÞ Wik ðsÞ TðsÞ
0 h n¼1

jWik(T)i is that at the target final time t = T. On the other hand, jUfki
  )
is the kth final target wavefunction at time t = T. Our purpose is to @
þ dWfk ðsÞ Wik ðsÞ
maximize the objective function, J, at some given time T. We stress @s
that our purpose is to maximize J with T not being fixed. Note that Z 1 ( (*  " # +)
i 
 b X~ !
N
the objective functional given in Eq. (1) is different from that of þ ds 2Re Wfk ðsÞ H  ln  En ðsÞ dWik ðsÞ TðsÞ
the conventional MTOCT investigated so far. The usual objective 0 h n¼1

  
functional for MTOCT is given by [2,7,23]: @
Z 2Re Wfk ðsÞ dWik ðsÞ
X
z T @s
J¼ fjhWik ðTÞjUfk ij2 g  a0 jEðtÞj2 dt; ð2Þ (*  " # +)
i 
 b X~ !
N
k¼1 0
2Re Wfk ðsÞ H  ln  En ðsÞ Wik ðsÞ dTðsÞ
h n¼1

where E(t) is the external laser field and a0 is usually called the pen- (*   +) )#
i X N  !
alty factor that is used to minimize the fluence of the external fields.  
þ2Re Wfk ðsÞ l W ðsÞ  d En ðsÞTðsÞ
~
Note that our objective does not include the constraint of the pen- h n¼1 n  ik
alty factor. Defining the objective functional as Eq. (2) and adding Z 1
@
the constraint arising from the equations of motion that the quan-  dsmT ðsÞ dTðsÞ: ð7Þ
0 @s
tum system should obey, a monotonically convergent algorithm of
 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22 15

Next, we perform the following partial integrations: X

z
 


Z Z þ 2Re Ufk   Wfk ðs ¼ 1Þ jdWik ðs ¼ 1Þi
1 1
@ @ mT ðsÞ k¼1
mT ðsÞ dTðsÞds ¼ ½mT ðsÞdTðsÞss¼1
¼0  dTðsÞds "   
0 @s 0 @s X
z

 @ Wik ðs ¼ 1Þ
þ 2Re Wik ðs ¼ 1ÞjUfk Ufk j
¼ mT ðs ¼ 1ÞdTðs ¼ 1Þ  mT ðs ¼ 0ÞdTðs ¼ 0Þ Tðs ¼ 1Þ@ s
k¼1
Z 1
@ mT ðsÞ  mT ðs ¼ 1ÞdTðs ¼ 1Þ þ mT ðs ¼ 0ÞdTðs ¼ 0Þ: ð12Þ
 dTðsÞds ð8Þ
0 @s
For J to be maximized or minimized, we can deduce the following
and
*  + equations from  Eq. (12):
Z  @
b  PN ~
1 !


Wfk ðsÞ dWik ðsÞ ds ¼ Wfk ðs ¼ 1ÞjdWik ðs ¼ 1Þ h @ jW@iksðsÞi ¼ H
i n¼1 ln  E ðsÞ jWik ðsÞiTðsÞ subject to the ini-
0  @s tial condition
n

Z 1  
@ 
 Wfk ðsÞdWik ðsÞ ds: ð9Þ jWik ðs ¼ 0Þi ¼ jUik i; ð13Þ
0 @s
Here, we have used the fact that the initial states Wik(s = 0) are where jUiki is the
 initial given!state for the kth target.
 
fixed and so dWik(s = 0) = 0. @ jW ðsÞi
h @fks ¼ H
i b  PN ~ l  E ðsÞ Wfk ðsÞ TðsÞ subject to the ini-
n¼1 n n
Introducing Eqs. (8) and (9) into Eq. (7), we obtain: tial condition
X
z
 


dJ ¼ 2Re Wik ðs ¼ 1ÞjUfk Ufk jdWik ðs ¼ 1Þ 2 jWfk ðs ¼ 1Þi ¼ jUfk i; ð14Þ
k¼1
(*  " # +
  
P

b  PN ~
!
Z 1 i  @ mT ðsÞ
 b
X N !
 @s
¼  2h zk¼1 Im Wfk ðsÞ H n¼1 l n  E ðsÞ j Wik ðsÞ i subject to
 dsRe dWfk ðsÞ H ln  En ðsÞ Wik ðsÞ TðsÞ
~ n
0  h  the initial condition
n¼1
   ) Z 1 ( (* 
@ i X
z   

 @ Wik ðs ¼ 1Þ
þ dWfk ðsÞ Wik ðsÞ þ ds 2Re Wfk ðsÞ mT ðs ¼ 1Þ ¼ 2 Re Wik ðs ¼ 1ÞjUfk Ufk j ; ð15Þ
@s 0  h Tðs ¼ 1Þ@ s
" # +) (*  +) k¼1
XN !  @ 
 Hb ~ln  En ðsÞ dWik ðsÞ TðsÞ þ 2Re 
Wfk ðsÞdWik ðsÞ when Eqs. (13)–(15) are satisfied, we have:
n¼1
 @s 
(*  " # +) Z 1 X
N
i X N 
2Re

Wfk ðsÞ H b ~
!
ln  En ðsÞ Wik ðsÞ dTðsÞ dJ ¼ ds g n ðsÞdEn ðsÞ þ mT ðs ¼ 0ÞdTðs ¼ 0Þ; ð16Þ
 h n¼1
 0 n¼1
(*   +) )#
i X N  !

þ2Re Wfk ðsÞ ln Wik ðsÞ d En ðsÞTðsÞ
~ where we have defined
 h n¼1 
Z 1
@ mT ðsÞ 2X z

 
þ dTðsÞds  mT ðs ¼ 1ÞdTðs ¼ 1Þ þ mT ðs ¼ 0ÞdTðs ¼ 0Þ g n ð sÞ ¼  Im Wfk ðsÞln jWik ðsÞi TðsÞ: ð17Þ
@s h k¼1
0
X 

z

2 Re Wfk ðs ¼ 1ÞjdWik ðs ¼ 1Þ : ð10Þ If the correction of the laser amplitude En(s) is expressed as dEn(s),
k¼1
we define:
Because we can expect that jUfki ’ jWik(s = 1)i and that
 E  E dEn ðsÞ ¼ an g n ðsÞ: ð18Þ
@ Wik ðs¼1Þ @ W ðs¼1Þ ik ðs¼1Þi
 Tðs¼1Þ@ s ¼  ik@t ¼ jdW
dTðs¼1Þ
according to Eq. (3), we can rewrite
the first term of Eq. (10) as: On the other hand, if we define the correction of T(s) as dT(s), we


 choose:
2Re Wik ðs ¼ 1ÞjUfk Ufk jdWik ðs ¼ 1Þ

 dTðsÞ ¼ bmT ðs ¼ 0Þ: ð19Þ
¼ 2Re Ufk jdWik ðs ¼ 1Þ
(* +*  +)
 @ W ðs ¼ 1Þ If Eqs. (18) and (19) are inserted into Eq. (16), we find:
 ik
þ 2Re Wik ðs ¼ 1ÞjUfk Ufk  dTðs ¼ 1Þ: ð11Þ
 Tðs ¼ 1Þ@ s
X
N Z 1

Inserting this expression into Eq. (10), we obtain: dbJ ¼ an dsg n ðsÞ2 þ bmT ðs ¼ 0Þ2 : ð20Þ
0
"Z " (* ( " # n¼1
X
z 1  i X N !
 b
dJ ¼ ds 2Re dWfk ðsÞ H ln  En ðsÞ
~ If the parameters, an and b, are all positive, it is expected that
k¼1 0  h n¼1
 +) #  the objective reaches a maximum monotonically, as is clearly
 Z 1 
@  @ Wfk ðsÞ seen from Eq. (20). On the other hand, if they are all negative,
þ Wik ðsÞ TðsÞ þ ds2Re
TðsÞ@ s  0 @s  it is expected that the objective reaches a minimum monotoni-
*  " # ) +# cally.
i XN ! 

 Wfk ðsÞ b
H ln  En ðsÞ TðsÞ dWik ðsÞ
~ Summarizing, from the above derivation, we propose the fol-
 h n¼1
 lowing algorithm to find the optimal external fields En(t) while
Z 1 (*  " # +)
i XN !  simultaneously allowing the final time to be free. In what follows,

2 dsRe Wfk ðsÞ H b ln  En ðsÞ Wik ðsÞ dTðsÞ
~ the superscript (j) is used to denote the quantity of the jth
0 h 
(* 
n¼1
+ ) # iteration.
Z 1 i X N !

þ2 dsRe Wfk ðsÞ ln jWik ðsÞ  d En ðsÞ TðsÞ
~ (i) One chooses initial guess external fields Eð0Þ
0  h n¼1 n ðsÞ for the nth

Z 1 molecule and the nominal T(0) that is the final time of

@ m T ð sÞ quantum dynamics. The trial positive parameters an and
þ ds dTðsÞ
0 @s b are given because our purpose is to maximize Eq. (1).
16 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22


(ii) The Schrödinger equations (Eq. (13)) for z targets are propa- Wfk ðsÞl1 cos h1 jWik ðsÞi
gated forward in time from s = 0 to s = 1 and the obtained X ðkÞ ðkÞ
 E ¼ l1 cj1 þ1;m1 ;j2 ;m2 ðsÞdj1 ;m1 ;j2 ;m2 ðsÞ
 ðjÞ
z wavefunctions Wik ðsÞ at each time s are stored. j1 ;m1 ;j2 ;m2
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
At the same time, the objective functional J ðjÞ ¼ ðj1 þ m1 þ 1Þðj1  m1 þ 1Þ
Pz D ðjÞ E2 
 ð2j1 þ 1Þð2j1 þ 3Þ
k¼1  Wik ðTÞjUfk  is calculated. sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
(iii) Eqs. (14) and (15) are propagated backward
 in
E time from X ðkÞ ðkÞ ðj1 þ m1 Þðj1  m1 Þ
þ l1 cj1 1;m1 ;j2 ;m2 ð sÞdj1 ;m1 ;j2 ;m2 ð sÞ
s = 1 to s = 0 and the z wavefunctions WðjÞ
fk ðsÞ are stored. ð2j1  1Þð2j1 þ 1Þ
;
j1 ;m1 ;j2 ;m2
In addition, mT(s = 0) is calculated.

(iv) Using Eqs. (18) and (19), the laser amplitude EðjÞ (j) and Wfk ðsÞl2 cos h2 jWik ðsÞi ¼ l2
n ðsÞ and T sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
are updated as follows: X ðj2 þ m2 þ 1Þðj2  m2 þ 1Þ
ðkÞ ðkÞ 
 cj1 ;m1 ;j2 þ1;m2 ð s sÞ
Þdj1 ;m1 ;j2 ;m2 ð
ð2j2 þ 1Þð2j2 þ 3Þ
Eðjþ1Þ
n ðsÞ ¼ EðjÞ
n ðsÞ þ an g n ðsÞ ð21Þ j1 ;m1 ;j2 ;m2
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
X ðkÞ ðkÞ ðj2 þ m2 Þðj2  m2 Þ
and þ l2 cj1 ;m1 ;j2 1;m2 ðsÞdj1 ;m1 ;j2 ;m2 ðsÞ :
j1 ;m1 ;j2 ;m2
ð2j2  1Þð2j2 þ 1Þ
T ðjþ1Þ ¼ T ðjÞ þ bmT ðs ¼ 0Þ: ð22Þ ð29Þ
(v) One sets the convergence criterion g and if the following
criterion: As is evident from Eq. (29), because the laser polarizations are as-
sumed to be parallel to the z-axis, only the principal rotational
  quantum numbers, j1 and j2, are changed by the incident laser
 ðjþ1Þ 
J  J ðjÞ  6 g; ð23Þ
pulses following the rotational selection rule: D j = ±1. Furthermore,
note that the laser pulse changes only the quantum numbers of
is met, the calculation is terminated.
each molecule, as is clearly seen from Eq. (29). The laser pulses can-
(vi) If the convergence is not sufficient, one updates EðjÞ n ðsÞ and
not change the quantum numbers of respective molecules simulta-
T(j) to Eðjþ1Þ
n ðsÞ and T(j+1), and loops back to step (ii).
neously. This means that the laser pulses affect their respective
systems only locally, not globally. Therefore, the incident laser
To apply the theory developed above and demonstrate
pulses cannot change the entanglement degree in the absence of
numerical results, we take quantum computing using the rota-
entangling interactions. In the case of rotational qubits of mole-
tional modes of two polar molecules coupled by dipole–dipole
b is ex- cules, the entanglement degree can only be changed by rotational
interaction as an example. In this case, the Hamiltonian H
dipole–dipole coupling among molecules. Note that dipole–dipole
pressed as:
coupling also changes the magnetic quantum numbers m in addi-
b ¼H
b0 þ V
b; tion to the principal quantum numbers j, which is determined by
H ð24Þ b . This will cause depopulation from our two-qubit
the form of V
b 0 denotes the diagonal part of the Hamiltonian, which space of interest.
where H
The flowchart of the two-state Deutsch–Jozsa algorithm that is
satisfies:
the purpose of our calculations in the following section is shown in
 Fig. 1. The Deutsch–Jozsa algorithm can be described as follows. Let
b 0 jj ; m1 ; j ; m2 i ¼ 1 1
H 1 2 j1 ðj1 þ 1Þ þ j2 ðj2 þ 1Þ jj1 ; m1 ; j2 ; m2 i; us define the person who holds the query register as Alice, while
2I1 2I2
the person with the answer register is Bob. The purpose of this
ð25Þ algorithm is to allow Alice to determine whether the function f that
Bob manipulates, which is contained in the oracle denoted by Uf in
where Ii represents the rotational constant for the ith molecule
the figure, is either constant or balanced. It is known that the algo-
and ji and mi denote the rotational principle and magnetic
b is the rithm scales as O(2n) classically, while it scales quantum-mechan-
quantum numbers of the ith molecule, respectively. V
ically as O(n), where n is the number of qubit registers that Alice
rotational dipole–dipole coupling operator, which can be written as:
holds. This demonstrates the significant speedup of quantum par-
n o allelism compared with classical algorithms.
b ¼ l1 l2 1 ~
V v 1  v
~ 2  3ðv
~ 1  b ~
RÞð v 2  b ;
RÞ ð26Þ The details of the two-state Deutsch–Jozsa algorithm are as fol-
4pe0 R3
lows. Let us assume that Alice holds the control qubit while Bob
holds the target qubit as shown in Fig. 1. The initial state of the
where l1 and l2 are the dipole moments for the first and second
whole Hilbert space is j00i, where the first entry denotes the state
v i is the unit vector of the orientation of
molecules, respectively, ~
of the control qubit and the second entry denotes that of the target
the ith molecule, R is the distance between the two molecules,
b is the unit vector from the center of the first molecule to qubit. First, Bob applies the NOT gate, and the transition j00i
and R
? j01i takes place. Bob then applies the Hadamard gate Hdm1
the second molecule.
and Alice applies the Hadamard gate Hdm2. At this stage, the state
The wavefunctions are explicitly expressed as:
of the whole system becomes j00i  j01i + j10i  j11i. The unitary
j1
X X j2
X X ðkÞ
transformation, the so-called oracle,
jWik ðsÞi ¼ cj1 ;m1 ;j2 ;m2 ðsÞjj1 ; m1 ; j2 ; m2 i; ð27Þ
j1 ¼0 m1 ¼j1 j2 ¼0 m2 ¼j2 U f : jx; yi ! jx; y  f ðxÞi; ð30Þ
j1 j2
  X X X X
Wfk ðsÞ ¼ ðkÞ
dj1 ;m1 ;j2 ;m2 ðsÞjj1 ; m1 ; j2 ; m2 i; ð28Þ is then applied to this state by Bob. Here,  denotes addition
j1 ¼0 m1 ¼j1 j2 ¼0 m2 ¼j2
modulo 2. The rule of Eq. (30) must be applied for all four possible
ðkÞ ðkÞ
where cj1 ;m1 ;j2 ;m2 ðsÞ and dj1 ;m1 ;j2 ;m2 ðsÞ are the time-dependent coeffi- definitions of f, where f1, f2, f3 and f4 are ID, NOT, CNOT, and ACNOT
cients for the laser-driven wavefunctions jWik(s)i and jWfk(s)i, gate operations, respectively. Here, ID and NOT gates are related to
respectively. The matrix elements of the electric dipole interaction the constant function and CNOT and ACNOT gates are related to
are explicitly given by: the balanced function. According to the four definitions, the state
 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22 17

Fig. 1. Flowchart of the two-state Deutsch–Jozsa algorithm.

j00i  j01i + j10i  j11i is changed to j00i  j01i + j10i  j11i,

j00i + j01i  j10i + j11i, j00i  j01i  j10i + j11i, and j00i +
j01i + j10i  j11i, respectively. Then, Alice applies the Hadamard
transformation, Hdm2. This transforms the states j00i  j01i +
j10i  j11i, j00i + j01i  j10i + j11i, j00i  j01i  j10i + j11i, and
j00i + j01i + j10i  j11i into j00i  j01i, j00i + j01i, j10i  j11i,
and j10i + j11i,respectively. Finally, if she obtains the state j0i,
then f is constant, and if she obtains the state j1i, then f is balanced.
These states can be distinguished by measuring her own qubit, as
shown at the end of the flowchart in Fig. 1.

3. Numerical results and discussion

The purpose of the following calculations is to apply our FRTP-

MTOCT algorithm derived above to constructions of quantum gate
pulses and to show the advantage of our theory. To do so, we con-
centrate on constructions of elementary quantum gates involved in
the Deutsch–Jozsa algorithm using rotational modes of two NaCl
molecules coupled by dipole–dipole interactions and compare
the new results with those obtained previously using the conven-
tional MTOCT [12]. We assume that the state with quantum num-
bers j = 0, m = 0 is the conventional qubit state j0i and the state
with j = 1, m = 0 is j1i for simplicity. The Hilbert space spanned
by these eigenstates of two molecules is our two-qubit system.
In addition, we used all of the gate pulses obtained in [12] as the
initial guess pulses in the following calculations because we have
already obtained good transition probabilities and fidelities using
those gate pulses.
In the present paper, we investigate two configurations of two
polar molecules that are shown in Fig. 2. When the rotational axes
are numbered as (i) for each molecule, the interaction between the
two molecules is attractive; when they are numbered as (ii), the
interaction is repulsive. Note that the linearly polarized laser polar-
izations are parallel to the z-axis that is the rotational axis of the
molecules.
Because our purpose is to compare the calculation results dem-
onstrated in [12] with those evaluated by FRFP-MTOCT, the param-
eters pertaining to the quantum system should be the same in both
cases. Therefore, the calculation procedures adopted in the present
work are the same as those used in [12]. However, we concentrate
on the NaCl molecules because we obtained better results for the
NaBr molecules and there may be room to improve for the NaCl
molecules. For clarity, we repeat details of the molecular parame-
ters and calculation method here. The NaCl molecules consist of
the isotopes, 23Na and 35Cl. The dipole moment of NaCl (8.388 D)
Fig. 2. Two configurations of two polar molecules coupled by dipole–dipole
e is the laser polarization, and c is
interaction. R is the intermolecular distance, ~
the molecule-fixed coordinate parallel to the dipole moment. For details, see the
text.
was calculated using the B3LYP level of theory and the basis set
6-31G (2df,p) [34]. The equilibrium bond length Re is 2.3612 Å
for the NaCl molecule. The time propagation of the time-dependent
Schrödinger equations was performed using the fourth-order Run-
ge–Kutta algorithm. The propagation time step was ds = 6.104 
105 or ds = 1.221  104. The interval between the two molecules,
R, was set to 5 nm. The parameters a1 and a2 were set to be
1.755  105  3.510  105 W/cm2 and b was set to 0.00–
5.85  103 ps2. In the following, we show numerical results and
discuss them.
First, let us concentrate on Fig. 3. Panel (a) compares the transi-
tion probabilities for FRFP-MTOCT and FIFP-MTOCT versus itera-
tion number for various values of b when the Hdm2 gate pulses
are optimized. As expected, the transition probabilities converge
monotonically for any positive values of b. In addition, we note that
the rate of convergence is faster and the transition probabilities are
larger when b is larger. For any number of iterations, the transition
probability is greater for FRFP-MTOCT than for FIFP-MTOCT. In
particular, the highest transition probability is 0.964450492 when
b is equal to 5.85  103 ps2. This figure amounts to the highest
18 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22

Fig. 3. (a) Monotonic convergence of transition probabilities calculated using FRFP-MTOCT and FIFP-MTOCT with various values of b for the Hdm2 gate pulses shown in Fig. 1.
Note that the convergences of FRFP-MTOCT are better than those of FIFP-MTOCT. (b) Temporal durations of the Hdm2 gate pulses versus iteration number for various values
of b. The optimized temporal duration is shorter than the nominal one in all cases. The molecules are in the repulsive configuration, and a1 and a2 are equal to
1.755  105 W/cm2 and 3.510  105 W/cm2, respectively.

probability of reaching the target state investigated in the present
work. On the other hand, if optimization of the temporal duration
of the laser pulse is not allowed (i.e., b is equal to 0.00 ps2), the
transition probability amounts to 0.964340618. This figure is a
little smaller than the former case. On the other hand, panel (b)
shows temporal durations of the optimized laser pulses versus iteration
number for various values of b. We note that T becomes smaller
with increasing values of both iteration number and b. This implies
that the nominal temporal duration of the laser pulse, 5242.56 ps,
was a little too long for better target population transfer. The best
temporal duration, T, was estimated to be 5242.36085 ps when b
was equal to 5.85  103 ps2. This optimized laser pulse is employed
for simulation of the two-state Deutsch–Jozsa algorithm. Summarizing,
the FRFP-MTOCT developed in this work is more efficient than
FIFP-MTOCT.
In Fig. 4, we show the ratio of the optimized T to the nominal
T(0), T/T(0), for each gate pulse involved in the two-state Deutsch–
Jozsa algorithm shown in Fig. 1. From panel (a), a general tendency
is found that the optimized T becomes shorter if the nominal T(0) is
long and that the optimized T becomes longer if the nominal T(0) is
short. In particular, the Hdm2 gate shows this tendency promi-
nently. The ID gate is an exception: although the nominal T(0) is
short, the optimized T becomes shorter. These calculation exam-
ples appeal to our intuition: the optimal temporal duration does
not need to be too long but should be long enough to reach the
objective target state because the optimal temporal duration of
the laser fields exists for a specific quantum process. The present
example shows that the optimal temporal duration lies in the
range from 2621 to 5243 ps. On the other hand, in panel (b), a sim-
ilar tendency is found also in the case of the attractive configura-
tion. The most prominent feature is that the optimal temporal
duration of the ACNOT gate pulse becomes much longer than the
nominal T(0) in any cases studied in this work. This also means that
the nominal T(0), 2621.12 ps, was too short to reach a high transi-
tion probability. As is shown later in Table 1, this leads to a transi-
tion probability higher than that studied in [12] for the transition
j00i + j01i + j10i  j11i ? j10i + j11i.
Fig. 5 shows the calculation results for the CNOT gate in the
repulsive configuration. Panel (a) also demonstrates the monotonic
convergence of FRFP-MTOCT during the optimization of CNOT gate

Fig. 4. Ratio of optimized T to nominal T(0), T/T(0), for each gate pulse involved in the two-state Deutsch–Jozsa algorithm. Panel (a) is for the repulsive configuration and panel
(b) is for the attractive configuration.
 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22 19

Table 1
Transition probabilities of the quantum gates of two NaCl molecules in the attractive configuration with R equal to 5 nm. The numbers in parentheses are those reported in our
previous work [12]. Constant and balanced functions can be distinguished correctly with an accuracy of at least 96.36549%.

Gates Population (%) f1 f2 f3 f4

(Operations)
NOT 96.80379
(96.75660)
Hdm1 97.92185
(97.92185)
Hdm2 95.84992
(95.84992)
Uf 96.31811 96.86525 95.77509 93.86138
(96.31001) (96.86674) (95.77509) (93.78875)
Hdm2 97.76741 97.76741 91.74780 91.74780
(97.76741) (97.76741) (91.74780) (91.74780)
(Measurements)
Correctness 98.71765 97.35375 97.27479 96.36549
(98.74721) (97.35856) (96.63346) (96.48216)

Fig. 5. (a) Monotonic convergence of CNOT gate laser pulses in the repulsive configuration, (b) optimized control gate laser pulse, and (c) optimized target gate laser pulse
with a1, a2, and b equal to 1.755  105 W/cm2, 3.510  105 W/cm2, and 2.926  104 ps2, respectively (black lines indicate initial guess pulses and red lines indicate
optimized pulses), (d) comparison between the optimized laser pulse and the initial guess laser pulse for the control gate within the range from 1250 to 1750 ps, and (e)
comparison between the optimized laser pulse and the initial guess laser pulse for the target gate within the range from 1250 to 1750 ps. (For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of this article.)
20 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22

laser pulses. On the other hand, panels (b) and (c) compare the
optimized laser pulse and the initial guess laser pulse for the con-
trol gate and the target gate, respectively. We can see a slight dif-
ference between the initial guess laser pulses and the optimized
laser pulses. To see the shapes of the optimized laser pulses in
more detail, we compare the control and the target laser pulses
in panels (d) and (e), respectively, within the range of 1250.0–
1750.0 ps. From panels (d) and (e), we can only see very slight dif-
ferences between the initial guess pulses and the optimized pulses
at first sight. However, because a2 is larger than a1, the target laser
pulse (panel (e)) changes more markedly than the control laser
pulse (panel (d)). In particular, the difference is more marked
around 1300 ps and after 1500 ps in panel (e). In addition, it should
be noted that the optimized laser pulses shift slightly to right rel-
ative to the initial guess laser pulses as shown in panels (d) and (e).
This is because the temporal duration of the optimized laser pulses
becomes slightly longer than that of the initial guess laser pulses:
T = 2621.12283 ps and T(0) = 2621.12 ps.
On the other hand, Fig. 6 shows the calculation results for the
Hdm2 gate in the repulsive configuration. Panels (a) and (b) com-
pare the optimized laser pulse and the initial guess laser pulse
for the control gate and the target gate, respectively. We can see
a slight difference between the initial guess laser pulses and the
optimized laser pulses, as in Fig. 5. Again, to see the shapes of
the optimized laser pulses in more detail, we compare the control
and the target laser pulses in panels (c) and (d), respectively, with-
in the range of 2500.0–3500.0 ps. Because a2 is larger than a1, the
target laser pulse (panel (d)) changes more markedly than the con-
trol laser pulse (panel (c)). In particular, the difference is more pro-
nounced from around 2500.0 ps to 3000.0 ps in panel (d). In
addition, it should be noticed that the optimized laser pulses shift
slightly to the left relative to the initial guess laser pulses, as shown
in panels (c) and (d). This is because the temporal duration of the
optimized laser pulses becomes slightly shorter than that of the
initial guess laser pulses: T = 5242.36085 ps and T(0) = 5242.56 ps.
Because similar tendencies were found for the other gate laser
pulses and population transfers, the details for the other gate laser
pulses are not shown here.
Finally, we concentrate on Tables 1 and 2. These tables summa-
rize the population transfer probabilities at each step of the two-
state Deutsch–Jozsa algorithm and the correctness of the measure-
ment results of Alice. First, we note that in both tables almost all of
the population transfer probabilities at each gate were enhanced
compared with those reported in our previous work. Only a few
population transfer probabilities decreased slightly in comparison
with those calculated in our previous work. This may be because
we cannot determine which transition probability should be en-
hanced in our FRFP-MTOCT, as can be seen from Eq. (1). Therefore,
the cases of decreased transition probability increase the other
transition probabilities not involved in the two-state Deutsch–
Jozsa algorithm. If we look into the correctness of the measurement
results of Alice, it decreases a little in comparison with our previ-
ous results, contradicting the better population transfer probabili-
ties at each gate. This may also be caused by the fact that the ratio
of the final populations in the states j0i and j1i could not be better
because our FRFP-MTOCT cannot necessarily control the ratio.
Although our FRFP-MTOCT did not work well from the viewpoint
of the correctness of the measurement results of Alice in the
two-state Deutsch–Jozsa algorithm, the optimized gate laser pulses
of each gate in the present calculation may be utilized in other pro-
posed quantum computing algorithms such as Shor’s algorithm,
Grover’s algorithm, and so on.

Fig. 6. (a) Optimized control gate laser pulse and (b) optimized target gate laser pulse with a1, a2, and b equal to 1.755  105 W/cm2, 3.510  105 W/cm2, and
5.85  103 ps2, respectively, for the Hdm2 gate laser pulses in the repulsive configuration (black lines indicate initial guess pulses and red lines indicate optimized pulses), (c)
comparison between the optimized laser pulse and the initial guess laser pulse for the control gate within the range from 2500 to 3500 ps, and (d) comparison between the
optimized laser pulse and the initial guess laser pulse for the target gate within the range from 2500 to 3500 ps. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
 K. Mishima, K. Yamashita / Chemical Physics 379 (2011) 13–22
Table 2
Transition probabilities of the quantum gates of two NaCl molecules in the repulsive configuration with R equal to 5 nm. The numbers in parentheses are those reported in our
previous work [12]. Constant and balanced functions can be distinguished correctly with an accuracy of at least 97.51295%.
Gates Population (%) f1
(Operations)
NOT 96.98800
(96.97287)
Hdm1 98.08934
(98.03552)
Hdm2 95.76569
(95.71487)
Uf 95.40280
(95.28235)
Hdm2 96.36443
(96.30038)
(Measurements)
Correctness 98.42634
(98.43925)
From the above numerical results, we can conclude that FRFP-
MTOCT can modestly improve the optimized laser pulses tailored
by the conventional FIFP-MTOCT because the temporal duration
of the laser pulses can also be optimized accurately, which makes
OCT more flexible.
4. Conclusion
In the present paper, we have constructed FRFP-MTOCT for
quantum systems. To show that it does work, we have demon-
strated some of the numerical results comparing those calculated
using FRFP-MTOCT with those calculated using the conventional
FIFP-MTOCT. The quantum system chosen for numerical calcula-
tions was the rotational modes of two polar NaCl molecules
coupled by dipole–dipole interaction. From the numerical calcula-
tions, we have found that FRFP-MTOCT can modestly improve the
optimized laser pulses tailored by the conventional FIFP-MTOCT.
The features of our FRFP-MTOCT are the optimization of external
time-dependent perturbations (especially laser pulses) with high
transition probabilities, that of the temporal duration, the mono-
tonic convergence, and the ability to optimize multiple laser pulses
simultaneously. In particular, the most prominent feature of our
FRFP-MTOCT is that the objective can be maximized while the ex-
act temporal duration of the external perturbations can also be
determined at the same time. In conventional FIFP-MOCT, the tem-
poral duration is fixed and one cannot be confident that the initial
guess of temporal duration is optimal and so must try various ini-
tial guesses [11]. However, this is not necessary using our theory.
Our theory is more advantageous than conventional OCT in this
respect.
In the calculation examples shown above, extremely modest
improvements in gate fidelities were obtained by using our theory.
However, it should be noted that this slight improvement is very
important in quantum computing as was investigated in detail pre-
viously by taking vibrational qubits as an example by Babikov [15].
In future, large-scale quantum algorithms involving a number of
quantum gates may be found and will be proved to be much more
efficient than classical algorithms. In such a case, a slight improve-
ment of each gate will improve the final measurement results to a
great extent. Therefore, even minor readjustment of the gate pulses
tailored by the conventional MTOCT using our algorithm will be
valuable in quantum computing.
As shown in an overview paper [35] and publications therein,
different times for light fields can be found that yield to a high
quantum yield. In this work, the time duration was changed manually
and the optimal time was defined as the time leading to non-complex
structured quantum gate light fields, basically cooperating with
21
f2 f3 f4
96.37756 97.42317 96.85002
(96.38305) (97.43790) (96.79535)
96.36443 95.54258 95.54258
(96.30038) (95.54168) (95.54168)
97.51295 99.05331 98.38953
(97.61513) (99.01165) (98.47337)
the given molecular properties by allowing the external electric
field to readjust. But it should be noted that the temporal duration
of the light fields is fixed in the conventional FIFP-OCT and the
optimization degree of freedom is enhanced in the FRFP-OCT
because the temporal duration can be changed in the latter theory.
Therefore, it is reasonable that minor readjustment of the high-
fidelity gate pulses tailored by the conventional MTOCT using our
algorithm was obtained as demonstrated in the text.
Finally, we would like to make some comments on alternate
choices of the methods of optimization. Decreasing of an slows
down the convergence rate versus iteration number, as can easily
be understood from Eq. (18). This tendency corresponds to
decreasing of a0 in the conventional FIFP-OCT [36]. In addition, it
was noted that the convergence rate becomes much faster and
the transition probabilities become much larger when b is larger,
as was shown in Fig. 3. Further, it should be noted that because
the computational algorithms are different between our algorithm
and the conventional FIFP-OCT but because the choices of the
parameters are somewhat arbitrary in both of the methods,
significant or comparable improvements may be possible within
FIFP-MTOCT simply through the appropriate choice of the penalty
factors, a0 and an. Although our theory is the same as the Krotov
method with respect to no penalty factor and gradient method,
the former is more flexible and promising for obtaining the better
optimization probability because the temporal duration can be
altered during the optimization process, as mentioned in the last
paragraph.
Although we have used two polar NaCl molecules as a particular
quantum system for numerical demonstrations of our theory, the
theory is so general that it may be possible to apply it to a variety
of control problems in quantum dynamics in the future.
Acknowledgements
The authors thank CREST, JST for funding.
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