2
r
2
_ _
. 2
Since the timedependent perturbation does not depend on
the angle q
m
, m is a constant of the motion, and the mag
nitude of the moleculeeld interaction is largest for
m = 0. In this specic case the Hamiltonian is
H
j
2
2I
gtDxcos
2
q
j
; 3
equivalent to a planar (2D) rotor. This timedependent sys
tem can be studied in an extended phase space (j, q
j
, t, p
t
)
with Hamiltonian
K
j
2
2I
gtDxcos
2
q
j
p
t
; 4
where the time is now the auxiliary progress parameter s,
and the associated canonical equations are:
dt
ds
oK
op
t
1; 5a
dp
t
ds
oK
ot
2Dxt t
0
r
2
gt cos
2
q
j
; 5b
dq
j
ds
oK
oj
j
I
; 5c
dj
ds
oK
oq
j
gtDxsin 2q
j
. 5d
Since K is independent of s its value is conserved by the
time evolution (5). Setting K = 0, Eq. (4) gives
p
t
H
j
2
2I
gtDxcos
2
q
j
; 6
which yields the energy of the system at any time and pro
vides the initial condition for p
t
.
2.2. Classical interaction picture
The form of the Hamiltonian (1) allows the separation
H H
0
j H
1
u; t; 7
where H
0
is the freerotor Hamiltonian, H
1
contains the
interaction with the pulse, and we set u q
j
. In the classical
interaction picture (CIP) the dynamical variables evolve
forward in time according to the full Hamiltonian H then
backward in time using the Hamiltonian H
0
[24]. The Ham
iltonian in the CIP is obtained by a canonical transforma
tion using an F
3
j; u; t generator [25], an explicit function
of the old momentum j, the new angle u, and the time t
F
3
j; u; t j u Bj
2
t t
0
. 8
For this generating function we have [25]
j
oF
3
o u
j; 9a
u
oF
3
oj
u 2Bjt t
0
; 9b
H H
oF
3
ot
H Bj
2
gtDxcos
2
u
2Bjt t
0
. 9c
For the CIP Hamiltonian (9c) the equations of motion are
d u
dt
oH
oj
2Bt t
0
gtDxsin 2 u 2Bjt t
0
; 10a
dj
dt
oH
o u
gtDxsin 2 u 2Bjt t
0
10b
with the additional equation
dp
t
dt
oH
ot
g
0
tDxcos
2
u 2Bjt t
0
2BjgtDxsin 2 u 2Bjt t
0
. 11
C.A. Arango et al. / Chemical Physics Letters 420 (2006) 296303 297
The equation of motion for the stability matrix M [26] is
dM
dt
JHM; 12
with J the fundamental symplectic matrix, and H the hes
sian matrix of the Hamiltonian.
2.3. Semiclassical quantized actions and energies
For simplicity, we shall consider the planar (2D) rotor
only, both in classical and quantum mechanics, for which
the Hamiltonian is identical to (3). For the 2D rigid rotor
the semiclassically quantized actions are [3]
j mh; m 0; 1; 2; . . . 13
with energy levels given by
E
j
2
2I
m
2
h
2
2I
. 14
Precise knowledge of the angular momentum j implies
complete uncertainty in the conjugate angle variable q
j
(u)
[3,12]. The semiclassical analogue of the 2D quantum state
jj is the circle j = const., with angle u uniformly distrib
uted between 0 and 2p, 0 6 u 6 2p.
The system described by Eq. (3) is essentially a free rotor
for times t t
0
 )r. Rotational excitation is then studied
classically by computing the time evolution of an ensemble
of initial conditions associated with a given quantum state
from a time well before (t !1) to a time well after
(t !+1) the arrival of the laser pulse. Final j values for
individual trajectories in the ensemble will be constant and
excitation/deexcitation probabilities can be determined.
To calculate rotational excitation probabilities using the
primitive semiclassical Smatrix approach it is necessary to
identify all root trajectories [12], those trajectories which
start with quantizing actions j
i
and end up with quantized
nal actions j
f
as t !+1. In Fig. 1, we show nal mani
folds u
f
(u
i
) and j
f
(u
i
) corresponding to initial state j
i
= 0.
The initial manifolds are shown as dotted lines: the line
u = u
i
for the upper panel, and j = 0 in the lower one. Note
that, although in the second panel the root trajectories for
j = 16 are close to momentum space caustics, strictly
necessitating a uniform SC treatment [27], there are no dif
culties associated with fractal structure due to chaotic
scattering (chattering [28,29]).
2.4. Semiclassical Smatrix expression for rotational
transition amplitudes
Semiclassical transition amplitudes in the angular
momentum representation are obtained from integral rep
resentations of the form [12]
hj
f
je
i
Ht=h
jj
i
i
_
du
f
hj
f
ju
f
ihu
f
je
i
Ht=h
jj
i
i 15
with semiclassical wavefunction
hj
f
ju
f
i 2pih
1
2
e
iu
f
j
f
=h
. 16
Similarly the initial momentum to nal coordinate ampli
tude is given in terms of the coordinate (angle)
representation
hu
f
je
i
Ht=h
jj
i
i
_
du
i
hu
f
je
i
Ht=h
ju
i
ihu
i
jj
i
i. 17
The Van VleckGutzwiller semiclassical propagator in the
coordinate representation is [13]
hu
f
je
i
Ht=h
ju
i
i 2pih
1
2
r
o
2
F
1
u
f
; u
i
; t
ou
f
ou
i
1
2
exp
i
h
F
1
u
f
; u
i
; t i
p
2
m
r
_ _
. 18
with [25]
F
1
u
f
; u
i
; t
_
t
0
dt
0
j
t
0 _ u
t
0 H
t
0 19
and prefactor
o
2
F
1
u
f
; u
i
; t
ou
f
ou
i
1
2
ou
f
oj
i
1
2
. 20
2.5
2
1.5
1
0.5
0
0.5
f
/
20
15
10
5
0
5
10
15
20
2 1.5 1 0.5 0
j
f
i
/
Fig. 1. Propagated nal manifolds u
f
(u
i
) and j
f
(u
i
). Initial manifolds are
shown as dotted lines: u = u
i
(upper panel), and j = 0 (lower panel). In the
lower panel the lines at j = 16 are close to momentum space caustics.
298 C.A. Arango et al. / Chemical Physics Letters 420 (2006) 296303
There will in general be several distinct root trajectories
z
r
t
z
i
going from z
i
= (u
i
, j
i
) at time t = 0 to z
f
= (u
f
, j
f
)
at time t that contribute to the amplitude (18). (Note that,
although the semiclassical expressions given in this section
are implemented in the CIP, for notational convenience, we
use u rather than u to denote the CIP angle.)
The primitive semiclassical amplitude (18) diverges at
caustics (focal points), where
ou
f
oj
i
0. In order for the prim
itive semiclassical amplitude (18) to be valid for times after
the rst or any succeeding caustic, it is necessary to include
an extra timedependent phase (MorseMaslov index m
r
)
[13,30]. This phase changes only when the trajectory crosses
a caustic. (The time at which the kth caustic occurs, t
k
, is
called the kth focal time [19,31,13,32].) A general method
for computing such phases was given by Maslov [30]. Cam
polieti and Brumer [19] have given explicit and computa
tionally convenient formulas for general semiclassical
amplitudes [19]. Although there are simpler ways of includ
ing the correct phase when a caustic is crossed [16,17], these
are limited to systems with one degree of freedom. The for
mulas quoted in this section are the specialization to a single
degree of freedom of the general formulas given in Ref. [19].
Inserting (18) into (15) and evaluating the integral by
stationary phase, followed by substitution into (17) and a
change of variable to u
i
we obtain the IVR integral repre
sentation of the transition amplitude in the momentum
representation [14,19]
hj
f
je
i
Ht=h
jj
i
i 2ph
1
_
du
i
ou
t
ou
i
1=2
e
i
p
2
mu
i
;t
exp
i
h
F
2
u
f
; j
i
; t u
t
j
f
_ _
; 21
where [25]
F
2
u
f
; j
i
; t F
1
u
f
; u
i
; t j
i
u
i
. 22
and m(u
i
; t) is the Maslov index for the initial condition u
i
at time t
k
< t < t
k1
mu
i
; t
k
1 r
k
u
i
=2 23
with
r
k
u
i
lim
!0
sgn
ou
t
u
i
; j
i
ou
i
ou
t
u
i
; j
i
ou
i
_ _
1
_
_
_
_
_
_
24
and sgn is the sign function. That is, the Maslov index
changes after t
k
only if r
k
(u
i
) = 1, i.e., if
ou
t
ou
i
is negative
(positive) before t
k
and positive (negative) after t
k
. Since
this derivative cannot diverge this is equivalent to have a
trajectory crossing a caustic
ou
t
ou
i
0 at t
k
. Passage of the
derivative
ou
t
ou
i
through the value zero means that special
attention must be given to the continuity of the integrand
as a function of u
i
.
The computational advantage of formula (21) is that the
prefactor never diverges. Moreover, it is not necessary to
locate root trajectories, instead an integral over all possible
values of u
j,i
must be performed for each j
f
. Possible prob
lems arise from the fact that the integral (21) is oscillatory
and the square root is not necessarily a smooth function of
the initial angle. Note that the SCIVR result is not a uni
form SC approximation [5].
Evaluation of the integral (21) using the stationary
phase approximation gives the primitive semiclassical
(SCSPA) expression [19]
hj
f
je
i
Ht=h
jj
i
i 2pih
1
2
u
r
i
oj
t
ou
i
1
2
exp
i
h
F
4
j
f
; j
i
; t i
p
2
mu
i
; t
_ _
; 25
where the sum involves all the root trajectories with j = j
i
at
t = 0 and j = j
f
at the nal time, the generating function
[25]
F
4
j
f
; j
i
; t
_
t
0
dt
0
u
t
0
dj
t
0
dt
0
H
t
0
_ _
; 26
and the Maslov index for the ith root trajectory in
t
k
< t < t
k1
is [19]
mu
i
; t
1
2
1 sgn
oj0
ou
i
_ _
k
Dm
k
u
i
. 27
As the elapsed time passes through the value t
k
, the index
changes by an amount
Dm
k
u
i
lim
!0
1
2
r
k
1 sgn
oj
; j
ou
; 28
with u
u
t
u
i
; j
i
; j
j
t
u
i
; j
i
, and
r
k
u
i
sgn
oj
t
u
i
; j
i
ou
i
oj
t
u
i
; j
i
ou
i
_ _
1
_
_
_
_
_
_
. 29
Again the Maslov index changes only if r
k
(u
i
) = 1, but
now this change could be positive or negative depending
on the sign of the partial derivative in (28).
The total primitive semiclassical amplitude (25) is
obtained by adding the amplitudes of the root trajectories.
The probability of a transition from j
i
to j
f
is given by
P
j
i
!j
f
h
2
jhj
f
jj
i
ij
2
. 30
Use of Eq. (25) requires knowledge of all the root trajecto
ries. For a given j
i
and j
f
= J
f
these trajectories are obtained
from the curve j
f
(u
i
) as shown in Fig. 1, where we have
j
i
= 0 and r = 0.04. It can be seen that u
i
= 0, p/2, p, 3p/
2 are xed points of Eq. (10). Root trajectories for
j
f
= 16 are close to the momentum space caustics, while
the line j
f
= 0 has an inection point at u
i
% 0, p. For the
case j
f
= 10, for example, there are four root trajectories
with initial angles u
r
i
, r 2 {1, 2, 3, 4}. For each of the ini
tial conditions it is necessary to obtain, at the nal time, the
stability matrix component oj
t
/ou
i
, the accumulated value
of the line integral F
4
(dened in Eq. (26)), and also the
accumulated Maslov index mu
i
; t, obtained via Eqs.
C.A. Arango et al. / Chemical Physics Letters 420 (2006) 296303 299
27,27,29, and thereby calculate the associated complex
amplitude. In practice we interpolate the curves of nal
oj
t
/ou
i
, F
4
, and mu
i
; t at the root values of u
i
instead of
doing the calculation over for the root trajectories alone.
The calculation of the SCIVR transition probabilities pro
ceeds similarly; in this case the integral (21) over initial an
gles must be done.
A comparison of semiclassical and quantum results
(exact and within the sudden approximation) is given in
Section 4.
3. Quantum mechanical sudden approximation
For very short pulses (r (1/B) the use of the quantum
sudden approximation is appropriate [33]. The propagator
for Hamiltonian (1) over the time interval t = 0 to t = T,
where 0 6 t
0
6 T and the pulse intensity is practically zero
at 0 and T, is approximated as [20]
UT; 0 e
ib cos
2
u
e
iT
H
0
=h
; 31
where
H
0
is the Hamiltonian for the free 2Drotor and b is
obtained as
hb
_
T
0
gt
0
Dxdt
0
p
p
rDx; 32
for the Gaussian pulse described by (2), where we set the
integration limits to 1in evaluating the integral. For ini
tial state w
0
u 2p
1=2
e
ij
0
u
, the postpulse state is
w
t
u
UT; 0w
0
u e
ib cos
2
u
e
iTEj
0
=h
w
0
u. 33
Expanding in terms of rotor eigenfunctions w
j
(u) = (2p)
1/2
e
iju
, we have
w
t
u
j2Z
c
M
Tw
j
ue
iTEj=h
34
with coecients
c
j
T
1
2p
e
iTEjEj
0
=h
_
2p
0
e
ib cos
2
u
e
iuDj
du 35a
1
2
e
iTEjEj
0
=h
e
ib=2
i
Dj=2
JDj
2
b=21 e
ipDj
35b
where Dj = j j
0
and J
m
(z) is the usual Bessel function.
Associated probabilities for transitions j
0
!j are
P
j
0
!j
jc
j
Tj
2
1 cospDj
2
JDj
2
b=2
_ _
2
. 36
Thus, within the sudden approximation P
j
0
!j
0 if Dj is
odd. For Dj even, we have
P
j
0
!j
JDj
2
b=2
_ _
2
; Dj even. 37
The eectiveness of the sudden approximation for short
pulses is shown in Fig. 2. For a pulse of width r = 0.02
(upper panel) there is almost perfect agreement for all the
transition probabilities for small Dx. For larger values of
Dx the results of the approximation are slightly dierent
from the numerically determined (exact) quantum transi
tion probabilities [34]. For a longer pulse of width r = 0.04
(lower panel) the sudden approximation works well for
Dx < 200 but yields worse results for larger values of Dx.
4. Comparison of semiclassical and quantum results
To compare with dimensionless quantum results the
classical rotational constant is set to the value B = 1. For
the short pulses studied here we have r (1/Bh. Another
relevant parameter in the calculations is the dimensionless
interaction strength Dx, for which the physical range of
values is between 0 and 800 [23]. 5000 trajectories were
used to evaluate the SCIVR integral, 2000 trajectories
for the SPA calculation.
Fig. 3 shows primitive and SCIVR transition probabil
ities for a 2D rotor starting in the ground state j = 0 for the
case of an intense (Dx = 400) short pulse (r = 0.04h/B).
Both semiclassical methods obey the symmetry selection
rule Dj = 2 for the 2D rotor in a linearly polarized laser
eld [12]. In contrast to the IVR results, the primitive SC
0
0.2
0.4
0.6
0.8
1
P
0
,
J
J=0
J=2
J=4
QM
0
0.2
0.4
0.6
0.8
1
500 400 300 200 100 0
P
0
,
J
J=0
J=2
QM
Fig. 2. Comparison of quantum sudden approximation and exact
numerical quantum transition probabilities for short pulses. Initial state
J = 0. (Upper panel) r = 0.02. Sudden approximation and exact quantum
values are in good agreement for transition probabilities J = 0 !0, 0 !2
and 0 !4 for the range of laser intensities shown, 0 6 Dx 6 500. (Lower
panel) r = 0.04. For the longer pulses, the sudden approximation begins
to fail for Dx > 200.
300 C.A. Arango et al. / Chemical Physics Letters 420 (2006) 296303
approximation fails completely for the transition probabil
ities P
0!16
and P
0!0
due to the proximity of momentum
caustics.
For the parameters of Fig. 3, the primitive semiclassical
results are in better agreement with the exact quantum
results than the SCIVR for several nal J values. Fig. 4
provides a more global picture for pulses of width r =
0.04 and 0.08, and clearly shows the overall superiority
of the SCIVR method. The longer pulses (r = 0.08) lead
to more complicated caustic structure of the nal mani
folds, so that the primitive SC method essentially fails
completely.
5. Semiclassical angular focussing of 2Drotors
As the laser pulse reaches its maximum intensity at
t = t
0
the rotor is subject to a strong periodic doublewell
potential in the angle u with maxima at u = p/2, 3p/2 and
minima at u = 0, p. For an initial quantized state with
small quantum number j, the pulse causes a localization
or focusing of trajectories near the minima of the poten
tial energy [18]. This focusing, among other phenomena,
has been studied recently for 2D and 3D kicked rotors
[18,22].
The primitive semiclassical approximation for the initial
momentum to nal coordinate amplitude [12] including the
Maslov index and considering all root trajectories is
0
0.2
0.4
0.6
0.8
1
P
0
,
0
a b
0
0.2
0.4
0.6
0.8
1
P
0
,
2
c d
0
0.2
0.4
0.6
0.8
1
500 400 300 200 100 0
P
0
,
4
e
500 400 300 200 100 0
f
Fig. 4. Primitive semiclassical (solid line), SCIVR (dashed line) and quantum (short dashed line ) P
0!J
rotational transition probabilities versus pulse
intensity Dx: (a) J = 0, r = 0.04; (b) J = 0, r = 0.08; (c) J = 2, r = 0.04; (d) J = 2, r = 0.08; (e) J = 4, r = 0.04; (f) J = 4, r = 0.08.
0
0.05
0.1
0.15
0.2
0.25
0 5 10 15 20
P
0
,
J
J
SCSPA
SCIVR
QM
Fig. 3. Primitive (SCSPA,       ), SCIVR semiclassical () and
quantum () rotational transition probabilities from the ground state
J = 0 for a 2D rotor in an intense, short laser pulse (Dx = 400, r = 0.04h/
B). The primitive transition probabilities at J = 0, 16 fail due to the
proximity to momentum caustics. Only probabilities for J P0 are shown;
for initial state J = 0, we have P
0!J
= P
0!J
.
C.A. Arango et al. / Chemical Physics Letters 420 (2006) 296303 301
hu
f
je
i
Ht=h
jj
i
i 2pih
1
2
r
ou
t
ou
i
1
2
exp
i
h
F
2
u
f
; j
i
; t i
p
2
mu
i
; t
_ _
38
with m(u
i
, t) given by Eq. (23).
The semiclassical initial state is the line of initial condi
tions with constant j
i
and 0 6 u
i
6 2p. This initial manifold
is propagated classically until time t = t
f
, when the curve
u
f
(u
i
) is used to obtain root trajectories corresponding to
a particular nal angle u
f
. Using Eq. (38) we obtain a semi
classical wave function at t = t
f
corresponding to the initial
state j
i
= J
i
h = 0. Fig. 5 shows associated probability densi
ties Pu jhuje
i
Ht=h
jj
i
ij
2
for a Gaussian pulse with
Dx = 400, r = 0.04h/B, centered at t
0
= 10 r. The primi
tive semiclassical propagation yields acceptable agreement
8 9 10
11 12 13
1
0.75
0.5
0.25
0


2
1
0.75
0.5
0.25
0


2
1
0.75
0.5
0.25
0


2
1
0.75
0.5
0.25
0


2
14 15 16
17
18
2 1.5
1 0.5 0
/
2 1.5
1 0.5 0
/
2 1.5
1 0.5 0
/
19
Fig. 5. Primitive semiclassical () and quantum (      ) probability densities for a 2D rotor initially in the ground state J = 0 subject to a pulse with
Dx = 400, r = 0.04 h/B. The legend for each panel indicates the elapsed time in units of the pulse width r. The center of the pulse is at 10r.
302 C.A. Arango et al. / Chemical Physics Letters 420 (2006) 296303
with the quantum results [34], and shows qualitatively the
focussing eect [18].
6. Conclusions
In this Letter, we have demonstrated the ecacy of stan
dard semiclassical methods [12] for analyzing rotational
excitation of nonpolar diatomic molecules (planar rotors)
by short nonresonant laser pulses. We have also investi
gated the applicability of the quantum mechanical sudden
approximation. Comparison with converged numerical
quantum results shows the sudden approximation to be
accurate for very short pulses (r = 0.02) but less accurate
for only slightly longer pulses (r = 0.04). Despite well
known failings of primitive semiclassical transition proba
bilities, the semiclassical IVR approach yields very accurate
results, even in a regime where the sudden approximation
fails. Finally, we have shown that primitive semiclassical
wavefunctions provide a qualitatively correct description
of angular focussing of rotational states by short laser
pulses [18].
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