A modified time-dependent perturbation approach to quantum dynamics and its

application to relaxation phenomena in magnetic molecules

C. A. Dartora, G. G. Cabrera, and K. Z. Nobrega

Citation: American Journal of Physics 77, 742 (2009); doi: 10.1119/1.3133088
View online: http://dx.doi.org/10.1119/1.3133088
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Published by the American Association of Physics Teachers

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A modied time-dependent perturbation approach to quantum dynamics
and its application to relaxation phenomena in magnetic molecules
C. A. Dartora
a
Departamento de Engenharia Eltrica, Universidade Federal do Paran (UFPR), Centro Politcnico,
Jardim das Amricas, 81531-990 Curitiba, Paran, Brazil
G. G. Cabrera
b
Instituto de Fsica Gleb Wataghin, Universidade Estadual de Campinas (UNICAMP),
13.083-970 Campinas, So Paolo, Brazil
K. Z. Nobrega
Departamento de Eletro-Eletrnica, Centro Federal de Educaco Tecnolgica do Maranho (CEFET-MA),
Av. Getulio Vargas 04, 65025-001 So Lus, Maranho, Brazil
Received 29 September 2008; accepted 21 April 2009
We introduce a modied version of the interaction picture applicable to situations in which the
nonperturbed Hamiltonian is time-dependent but can be diagonalized by the same basis of states at
all times. We probe the method using a simple model Hamiltonian to study the spin dynamics of
molecular magnets with time-dependent elds. Fully quantum mechanical calculations show the
superiority of our method compared to the usual time-dependent perturbation theory. Our approach
takes into account time-dependent elds and converges rapidly to the exact solution. 2009 American
Association of Physics Teachers.
DOI: 10.1119/1.3133088
I. INTRODUCTION
Time-dependent Hamiltonians are usually solved by time-
dependent perturbation theory in the context of the interac-
tion picture or the Dirac version of quantum mechanics.
1
The basic assumption in the usual interaction picture is that it
is possible to separate the Hamiltonian H into a nonper-
turbed time-independent part H
0
and a time-dependent per-
turbation Vt, which is assumed to be small. It is common
to say that the perturbation causes transitions between the
different eigenstates of H
0
see Ref. 2. The correct interpre-
tation describes the perturbed state as nonstationary, being a
coherent superposition of eigenstates of H
0
. This latter view
is adopted in this paper, where a key ingredient is the choice
of H
0
. We present examples of how to use this freedom for
choosing H
0
, which may include time-dependent terms.
Representative examples of time-dependent phenomena
include the dynamics of high-spin, high anisotropy molecu-
lar nanomagnets in the presence of time-dependent elds.
3
These systems are of much interest due to the occurrence of
magnetic hysteresis and the quantization of the magnetic
moment
3,4
and are ideal systems for illustrating how to treat
time-dependent elds.
5
Another interesting feature of molecular magnets concerns
the relaxation of spin states at low temperatures. The relax-
ation process is very slow and has been intensively studied
within the framework of LandauZenerStueckelberg
theory.
69
At low temperatures, quantum tunneling is of pri-
mary importance for relaxation because thermal activated
mechanisms for transition between magnetic states are neg-
ligible. In the adiabatic regime the LandauZener-
Stueckelberg theory predicts an exponentially small tunnel-
ing probability between states that are near a level crossing.
A more general treatment of time-dependent elds is desir-
able so that interesting physical phenomena with time-
dependent elds can be included.
9
Exact as well as accurate
approximate solutions
10
are superior to numerical approaches
because they allow us to understand qualitatively the basic
physics.
The usual low-order time-dependent perturbation theory
has several shortcomings. To lowest order the theory is lim-
ited to short time intervals, and the theory breaks down no
matter how small the perturbation near resonances. To over-
come those difculties, we introduce a modied version of
the interaction picture in which we split the Hamiltonian into
two time-dependent parts: the nonperturbed Hamiltonian H
0
is diagonalizable at all times by the same basis of states and
a perturbation Vt, which is usually not diagonal in the basis
of H
0
but is assumed to be small,
H= H
0
t + Vt. 1
We assume that H
0
t , H
0
t =0 for all t and t. H
0
in-
cludes contributions from time-dependent elds, which can-
not be considered as small. The perturbation Vt does not
necessarily commute with the unperturbed part, that is, in
general,
H
0
t, Vt 0 2
for all t and t.
We now solve the Schrdinger equation within this modi-
ed interaction picture. We introduce the unitary transforma-
tion
U
0
= exp

0
t
dtH
0
t

, 3
which transforms states and operators as

I
= U
0

, 4

I
= U
0

U
0
, 5
where the subscript I stands for interaction picture and kets
and operators without any subscript are understood to be in
742 742 Am. J. Phys. 77 8, August 2009 http://aapt.org/ajp 2009 American Association of Physics Teachers
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the Schrdinger picture. An observable O
I
obeys a
Heisenberg-like equation of motion with H
0
t,
dO
I
dt
=
1
i
O
I
, H
0
, 6
and the wave function
I
and the density matrix
I
evolve
according to Schrdinger-like equations with H
I
,
H
I

I
= i

I
, 7

I
t
=
i

I
, H
I
, 8
where H
I
is dened by
H
I
= U
0

VtU
0
= exp

0
t
dtH
0
t

Vtexp

0
t
dtH
0
t

.
9
The evolution of an initial ket-state
0
is given by the
unitary evolution operator U
I
in this modied interaction pic-
ture. The latter can be written in the form of a Dyson series
1
U
I
t, 0 = 1
i

0
t
dt
1
H
I
t
1

+
i

0
t
dt
1
H
I
t
1

0
t
1
dt
2
H
I
t
2
+ . . . , 10
with t
I
=U
I
t , 0
0
.
II. PROBING SPIN DYNAMICS
We now explore the method using Hamiltonians, which
describe the dynamics of molecular nanomagnets. A Hamil-
tonian used to model Fe
8
molecular clusters
1113
is given by
H= DS
z
2
+ ES
+
2
+ S

2
S Bt, 11
where D is the uniaxial anisotropy constant, E is the aniso-
tropy constant in the transverse plane, which may be small,
and S
z
, S

are the spin operators with units such that =1

S

=S
x
iS
y
. The effective Hamiltonian in Eq. 11 arises
from a complicated Hamiltonian of the form H=

1
2

i=1
N

j=1
N
J
ij

s
i

s
j

J
ij

is an exchange coupling matrix and

s
i

is the -component of the ith atomic spin operator in

which the spin interactions between the N individual atoms
composing the molecule are taken into account to obtain its
total effective spin S. The high anisotropy of the molecule is
a consequence of the interactions of many atomic spins. The
last term in Eq. 11 gives the coupling of the magnetic mo-
ment with a time-dependent magnetic eld Bt. If E=0, the
ground state would be doubly degenerate in the absence of
an external eld B, corresponding to the states with maxi-
mum parallel m=S and antiparallel m=S projections of
the magnetic moment along the quantization axis. The action
of E admixes these states with other states of the spectrum in
the sequence S , S2 , S4 , . . . S+4 , S+2 , S,
with a small coupling between S and S. As the value of
S increases, the coupling becomes weaker. For large aniso-
tropy, E/ D1, the spin up m0 and the spin down m
0 orientations of the molecular magnetic moment are
separated by an effective energy barrier, which is responsible
for the slow magnetic relaxation. At low temperatures, the
slow relaxation effects are due to tunneling through the bar-
rier.
As an example we consider spin 1 molecules S=1 under
the inuence of a time-varying magnetic eld along the
z-axis, which is taken as the quantization direction. The op-
erator S
z
is diagonal in the basis of states +1 , 0 , 1,
S
z
=

1 0 0
0 0 0
0 0 1

, 12
and the Hamiltonian Eq. 11 takes the form
H= DS
z
2
+ ES
+
2
+ S

2
B
0
tS
z
. 13
We rst solve Eq. 13 via the usual formulation of the in-
teraction picture, where the total Hamiltonian H is separated
as
H
0
= DS
z
2
+ ES
+
2
+ S

2
, 14
Vt = B
0
tS
z
. 15
We denote by s , 0 , a the basis that diagonalizes H
0
,
where 0 =m=0, and s , a correspond to the tunneling
states
s =
1

2
+ 1 + 1, 16
a =
1

2
+ 1 1. 17
The tunneling splitting is given by =2E, and the corre-
sponding eigenvalues of the energy are E
s
=D+, E
0
=0,
and E
a
=D. In this basis, ordered as s , 0 , a, the
time-dependent perturbation is nondiagonal
H
I
= B
0
tU
0

S
z
U
0
= B
0
t

0 0 e
2it
0 0 0
e
2it
0 0

,
18
where U
0

=expiH
0
t is the unitary operator that transforms
to the interaction picture.
If B
0
t =b
0
t, with b
0
being the sweep rate, the rst order
approximation of the evolution operator U
I
is
U
I
= 1 i

0
t
dtH
I
= 1 + ib
0

0 0 It
0 0 0
I

t 0 0

, 19
with
It =

0
t
dtte
2it
=
t
2i

1
4
2
e
2it

1
4
2
. 20
If we take the ground state a as the initial quantum state of
the molecule, it evolves according to the operator U
I
. The
evolution operator U
I
given by the innite Dyson series Eq.
10 is unitary, but because we truncate it to rst order, this
property no longer holds, and the norm of the initial state,
743 743 Am. J. Phys., Vol. 77, No. 8, August 2009 Dartora, Cabrera, and Nobrega
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a a =1, will be lost for the evolved state at later times. It is
convenient to renormalize the state according to the expres-
sion , t
I
=1/ aU
I

U
I
aU
I
a. The evolved and renor-
malized state for later times is given by
, t
I
=
1

1 +
2
b
0
2
I
2

a + ib
0
Is. 21
It is clear from Eq. 21 that without a renormalization
procedure, the norm of the state ket will diverge as t
because the tunneling amplitude increases without limit. That
means that a complete tunneling a s is accomplished at
asymptotically long times. The average of the spin projection
S
z
is
S
z
= , tS
z
, t =
2b
0
ImIte
2it

1 +
2
b
0
2
It
2

. 22
Note that the mean value S
z
is independent of the picture.
The average S
z
in Eq. 22 relaxes to zero at long times
because the asymptotic state s has zero magnetization.
We next perform the perturbation calculation via the modi-
ed version described in Sec. I and split the Hamiltonian H
as
H
0
t = DS
z
2
B
0
tS
z
, 23
Vt = ES
+
2
+ S

2
. 24
Note that H
0
t is diagonal in the S
z
-basis at all times. We
dene the operator U
0
=expi
0
t
dtH
0
t and express the
perturbation Hamiltonian H
I
=U
0

VtU
0
in matrix notation
as
H
I
= EU
0

S
+
2
+ S

2
U
0
= 2E

0 0
e
2i
0
t
dtB
0
t
0 0 0
e
2i
0
t
dtB
0
t
0 0

. 25
The evolution operator U
I
for the interaction picture is given
by
U
I
= 1 i

0
t
dtH
I
= 1 i

0 0 Jt
0 0 0
J

t 0 0

, 26
with the function Jt dened as
Jt =

0
t
dt exp

2i

0
t
dtB
0
t

. 27
If we again take the quantum state a as the initial state of
the molecule, we easily obtain the evolved state
, t
I
= U
I
a
=
1

21 +
2
J
2

1 + iJ+ 1 1 + iJ

1,
28
with Eq. 28 written in the S
z
-basis. To compare the results
we calculate the average value of the operator S
z
, which re-
sults in
S
z
= , t
I
S
z
, t
I
=
2 ImJt
1 +
2
Jt
2

. 29
If the eld is swept at a constant rate, B
0
t =b
0
t, the integral
in Eq. 27 can be expressed in terms of Fresnel integrals
14
Jt =

2b
0

1/2
Ct
2b
0

iSt
2b
0

,
30
with the asymptotic limits Cz 1/ 2 and Sz 1/ 2 for
z. There are damped oscillations in the magnetization
with the limiting value
S
z

2b
0
1 +

2

4b
0
, 31
showing that the system does not relax to the state of zero
magnetization. This behavior is very different from the be-
havior obtained in Eq. 22 using ordinary perturbation
theory. At small times, Eqs. 22 and 29 agree if we expand
both in a Taylor series and keep only the rst order terms. In
Fig. 1 we illustrate the superiority of the modied approach
by comparing both approximation methods with exact nu-
merical results for E/ D=0.05, and b
0
/ D
2
=0.1, correspond-
ing to an intermediate regime between the adiabatic and
nonadiabatic limits.
9,13
This example shows that our modi-
ed approach converges rapidly to the exact solution and
reliably reproduces the oscillations of the magnetization and
its asymptotic saturation value. In contrast, ordinary pertur-
bation theory is valid for only very short times. In our ap-
proach the time-dependent eld B
0
t =b
0
t is included in the
nonperturbed evolution operator U
0
=expi
0
t
dtH
0
t and
the evolved state will be correct to all orders of b
0
n
t
n
even in
the rst order approximation for U
I
. In contrast, the usual
perturbation method includes the time-dependent eld only
in the perturbed evolution operator U
I
, and the evolved state
Fig. 1. Time evolution of the magnetization S
z
t for E/ D=0.05 and
b
0
/ D
2
=0.1. We compare results from the modied perturbation theory
given by Eq. 29 solid line with exact numerical calculations dashed line
and with the usual perturbation theory given by Eq. 22 dotted line.
744 744 Am. J. Phys., Vol. 77, No. 8, August 2009 Dartora, Cabrera, and Nobrega
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will be correct only to rst order in b
0
t. At later times the
nonlinear terms b
0
n
t
n
for n2 will contribute signicantly to
the evolved state, which is why the usual perturbation theory
fails at later times.
III. CONCLUSIONS
We have developed a modied version of the interaction
picture suitable for problems in which a nonperturbed time-
dependent Hamiltonian H
0
t can be diagonalized at all
times by the same basis. In such cases, the results of the
modied perturbation method agree very well with the exact
solution even to the rst order and for very long times. We
note that the real-time dynamics of quantum states is impor-
tant for performing quantum computations, and several ap-
proaches have been proposed in the literature, including
elaborate numerical simulations.
15
Quantum bits qubits are
manipulated by time-dependent external elds. If large mag-
netic molecules are used to store quantum information, we
have to track the evolution of the states. As in any perturba-
tion approach, our method has a limited range of validity,
which depends on the relative magnitude of E, the transverse
anisotropy, and B
0
, the energy of interaction with the time-
dependent eld.
ACKNOWLEDGMENT
C.A.D. and G.G.C. would like to acknowledge partial -
nancial support from CNPq Conselho Nacional de Desen-
volvimento Cientco e Tecnolgico, Brazil through
projects 555517/2006-3 Edital MCT/CNPq 42/2006 and
304382/2005-1, respectively.
a
Electronic mail: cadartora@eletrica.ufpr.br
b
Electronic mail: cabrera@i.unicamp.br
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745 745 Am. J. Phys., Vol. 77, No. 8, August 2009 Dartora, Cabrera, and Nobrega
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