3rd International Conferences and Workshops on Basic and Applied Sciences 2010

ISBN: 978-979-19096-1-7

On the Origin of Inverted Modulation in HHG Signal of

Aligned CO2
Abdurrouf
Department of Physics
Brawijaya University, Malang, Indonesia
e-mail: abdurrouf@ub.ac.id
inverted compare with its alignment degree,

Abstract

cos 2

The paper investigates theoretically the high-order

harmonic generation (HHG) signal of aligned CO2
molecules and analyzes the origin of its inverted
modulation phase with respect to its alignment
degree,

cos 2

the angle between molecular axis and polarization

direction of pump pulse. In addition, the cut-off
position of CO2 can be extended or compressed
compare to that of its atom companion Kr, depends
on the peak laser intensity [10, 11].

. The analytical form of the

signal is derived by using the intense-field theory,

and expressed in term of some expectation values
of their higher moments. In this paper, the HHG
signal of aligned CO2 is evaluated by taking in
account the contribution from its HOMO (highest
occupied molecular orbital), as well as the
contribution from the two orbitals just below it,
referred as HOMO-1 and HOMO-2. It was obtained
that the dominant terms for HHG signal are
sin 2 ' cos 2 '

sin 2 '

, and

cos 2 '

The first experimental data on dynamics HHG

signal of CO2 was reported by Kanai et al. [6].
They observed the dynamic HHG signal as function
of pump-probe delay and compare the spectrum
with its ionization spectra. The HHG signal showed
a inverted modulation with respect to ionization
signal, i.e. the HHG yield is maximum (minimum)
when the alignment degree is minimum
(maximum). Later on, the inverted modulation in
plateau region was also reported in many
experiments [7-9, 128].

for HOMO, HOMO-1, and HOMO-2, respectively.

As

sin 2 '

In addition, Kanai et al. [6] also measured the top

signal (the HHG signal when its alignment degree
is maximum) and directly compared it with the antitop signal (the HHG signal when its alignment
degree is minimum) for various harmonic order in
plateau region. They obtained that the top signal
always smaller than the anti top signal meaning that
the inverted modulation is also kept for some
orders. For smaller and greater order, the top signal
increase whereas the anti top signal decrease and
they become close each other, suggesting a
possibility to get non-inverted HHG signal in lower
and higher order. Recently, the non-inverted HHG
signal was reported by Miyazaki et al. [9] in
perturbative region and Vozzi et al. [7, 8] near cutoff region.

is the only dominant term with

inverted modulation with respect to alignment

degree, it is instructive to conclude that the inverted
modulation phase in HHG signal of aligned CO2 is
due to the contribution of electron from HOMO-1.
Keywords: HHG
modulation, CO2.
1

signal,

alignment,

, depends on its order [69]. Here, is

inverted

Introduction

In recent years there has been much interest and

progress in understanding the interaction of atoms
and molecules with intense laser field (e.g. reviews
[1, 2]). In particular, is the observation of dynamic
alignments of the linear molecules N2, O2, and CO2
as function pump-probe delay time that are
monitored by the non-destructive high harmonic
generation signals induced by a delayed probe pulse
[35]. Among three molecules, CO2 shows richer
phenomena. In contrast to N2 and O2, the phase
modulation HHG signal of CO2 can be in same or

What is the origin of the phase difference between

HHG signal and ionization spectra in CO2? Kanai et
al. [6], Vozzi et al. [7], and Marangos [13]
attributed the inverted phase of HHG signal of CO2
as a manifestation of the interference in the
recombination process, known as quantum
interference. The correlation between quantum
interference and phase inversion in HHG of CO2
was confirmed by Vozzi et al. [7]. They measured
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Abdurrouf, On the Origin of Inverted Modulation in HHG Signal of Aligned CO2

HHG spectrum of both aligned and non-aligned

CO2. The minima were found in spectra of aligned
molecules but absent in one of non-aligned
molecules. They also obtained that the dynamics
spectra in minima region has inverted phase with
respect to alignment degree, while both have same
phase in the other region.

pump pulse (,), whereas the HHG operator is

given in frame of probe pulse (,) whose
polarization making angle with respect to the
pump polarization. Then we write the operator for
nth harmonic HHG signal as [21]:
Te( n ) (' , ' ; ) = 2n
)
(2)
l
x d 0lrm (' , ' ; ) nzz (l i , l r ; m )d 0im (' , ' ; )

The theoretical investigation by Le et al. [14] gave

another possible interpretation for the origin of
inverted modulation. By using Lewenstein model
[15] extended for molecules [16, 17], it was shown
that the inverted modulation is strongly related to
its alignment dependence. The HHG signal was
peaked at =45o for inverted modulation and at >
45o for non-inverted modulation. The dependence
of HHG peak of CO2 on harmonic order has also
been reported theoretically and experimentally [18,
19].

)
where nzz (l i , l r ; m ) is the dynamic part of the
electronic dipole, that depends on the initial angular
momentum li, the final angular momentum lr, and
the projection of the angular momentum of the
active electron along the molecular axis m. To
evaluate integral in Eq. (1), one must first transform
HHG operator from Te( n ) (' , ' ; ) to Te( n ) (, ; )
by using

The more recently proposed model by Smirnova et

al. [20], attributed the inverted phase modulation of
HHG signal of CO2 as due to the contribution of
multi orbital in generating HHG signal. As each
orbital has different symmetry, it has different
alignment dependence, and therefore gives a
specific dynamic HHG signal. The observed HHG
signal is combination of HHG signal from many
orbitals, with a specific competition between them,
depends on their ionization potential energy.

cos ' = cos cos + sin sin cos (3)

The purpose of this paper is to give an analytical

expression of HHG signal of aligned CO2, based on
the intense field theory [21]. The expression of
HHG signal from each orbital is derived, and it is
analyzed whether it has the same or different phase
modulation with respect the alignment degree. The
observed signal is then obtained by combining the
signal from all orbitals.

Figure 1: Modulus square of the asymptotic

form of the electronic wave function of CO2
For evaluating Eq. (1), we use the initial state of
molecular wave function given by
i (t ) = J 0 M 0 (t ) e (t ) ; i = (e, J 0 , M 0 ) (3)

which is consisting of the product of the ground

electronic e (t ) and the coherent rotational

2 Methodology
2.1
HHG signal of aligned Molecules
We start with briefly discuss the definitions of
HHG signal according to intense-field theory [21
23]. The HHG signal of aligned molecular
ensemble is given by
S (n ) (t d ; ) = C

J 0 M 0 (t ) . Here the electronic wave function can

be approximated by its asymptotic form

(ebf ) = C l( m ) Rl (r )Yl1 (r)

(4)

(J 0 )
J0M 0

x J 0 M 0 (t d , )Te( n ) (' , ' ; ) J 0 M 0 (t d , )

li l r

where R (r ) = r 1 e p B r is the radial part of the

(1)

wave function, where = Z C / p B is the core

charge and p B = 2 E B

with E B is binding

energy. For getting the alignment dependence of

HHG signal, the molecular wave function is
transformed from its body frame to fixed frame by
using the Wigner transformation matrix, whose

where C = (2 )2 (n / c )3 . In above, Te(n ) (' , ' ; ) ,

so called as the HHG operator for nth harmonic
generation, is a Fourier transform of electronic part
of the dipole of a single molecule whose electronic
wave function in body fixed frame. In general, the
rotational wave packet is given in the frame of

middle term, d 0lrm , appears in Eq. (2).

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3rd International Conferences and Workshops on Basic and Applied Sciences 2010

In this paper, we evaluate the HHG signal of

aligned CO2, by taking in account the contribution
from its HOMO, as well as the contribution from
the two orbitals just below it, referred as HOMO-1
and HOMO-2. The molecular properties of CO2 are
listed in Tab. 1, while the specific properties of
each orbitals are listed in Tab. 2. The modulus
square of asymptotic wave function of each orbitals
are shown in Fig. 1.

S H( n1) (t d , ) = C c H( n1),11 sin 2 '

Values
0.3902
4.01 - 4.11
1.97 1.93

+ ....

(6)

The last orbital contributing in generating HHG

signal is the HOMO-2, whose asymptotic electronic
wave function is modelled with l=1,3,5 and m=0
(see Tab. 2). The HHG signal due this orbital reads

S H( n2) (t d , ) = C c H( n2) ,11 cos 2 '

Table 1: Molecular properties of CO2: B is

rotational constant of molecule, whereas par
and perp are parallel and perpendicular
polarizability, respectively.
Properties
B (cm-1)
par (A3)
perp (A3)

ISBN: 978-979-19096-1-7

+ .... . (7)

Then the total calculated signal which is

comparable to the observed signal in the
experiment reads

Ref.
[24]
[25]
[25]

S H( n0) (t d , ) = C c H( n0) ,11 sin 2 ' cos 2 '

+ c H( n1),11 sin 2 '

Table 2: Molecular properties of CO2 which

depend on its orbital: Ip is adiabatic ionization

+ c H( n2) ,11 cos 2 '

potential, whereas C l(m ) are angular coefficient

(8)
2

+ ....

of the electronic wave function. H0, H1, and H2

stand for HOMO, HOMO-1, and HOMO-2,
respectively.
Properties
Symmetry
l
m
Ip (eV)
1st coeff.
2nd coeff.
3rd coeff.

H0
1g
2,4,6
1
13.8
1.97
0.40
0.04

H-1
1u
1,3,5
1
17.6
3.33
1.31
0.18

H-2
1u
1,3,5
0
18.1
7.50
2.58
0.32

Ref.
[26-28]
[26-28]
[26-28]
[28-29]
[28-29]
[28-29]
[28-29]

2.2. The calculated signal

We first evaluate the contribution from the highest
occupied molecular orbital (HOMO). The HOMO
of CO2 has 1g symmetry (see Fig. 1 and Tab. 2),
and we approximate its electronic wave function by
the asymptotic approximation, with m = 1 and l = 2,
4, 6 [28, 29], whose angular coefficients are
tabulated in Tab. 2. Then, by using the middle term
of the Wigner rotation matrix d 0lrm (available in
Refs, e.g. [30-32]) and simplifying them, we obtain
the corresponding HHG signal for CO2 due to its
HOMO as follow

S H( n0) (t d , ) = C c H( n0) ,11 sin 2 ' cos 2 '

Figure 2: The expectation values of first five

leading terms of HHG signal from HOMO of
CO2. The parameters are given in the text.

+ .... .(5)

The next contributing orbital in generating HHG

signal is the HOMO-1. By modelling its asymptotic
electronic wave function with l=1,3,5 and m=1 (see
Tab. 2), the HHG signal due this orbital reads

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Abdurrouf, On the Origin of Inverted Modulation in HHG Signal of Aligned CO2

Result

We first evaluate the phase of some expectation

values governing the HHG signal from the HOMO,
HOMO-1, and HOMO-2, respectively. In this work,
an ensemble of CO2 molecules was aligned by
using pump pulse of peak intensity 0.757 1014
W/cm2, pulse duration 60 fs, and at initial
temperature 200 K. The expectation values of first
five leading terms of HHG signal of aligned CO2
due to its HOMO are shown in Fig. 2. The figure
shows that the strongest term is the first one, that.
Taking in account that the cij coefficient in Eq. (5)
reduces by increasing i and/or j, one can conclude
that the contribution of HOMO is dominated by its
first term. The similar situation also occurs in
HOMO-1 and HOMO-2. Then we can approximate
the total HHG signal to be proportional to the sum
of the first term from each orbital, as expressed in
Eq. (7).
To get insight of the phase modulation of HHG
signal of each orbital, we then directly compare the
dominant terms of HOMO, HOMO-1, and HOMO2 with the alignment degree
Figure 3: The expectation values of first five
leading terms of HHG signal from HOMO-1 of
CO2. The parameters are given in the text.

cos 2

(t d ) ,

as

shown in Fig. 5. From the figure, one can see that

the dominant term of HOMO-1,

sin 2

(t d )

is

the strongest term and the only term has inverted

modulation with respect to the alignment degree.
This fact suggests us to deduce that the inverted
modulation of HHG signal of aligned CO2 is due to
the contribution of the signal of its HOMO-1.

Figure 5: The phase modulation of the dominant

term of HOMO, HOMO-1, and HOMO-2 (upper
panel), directly compare with the alignment
degree (lower panel). The parameters are given
in the text.

Figure 4: The expectation values of first five

leading terms of HHG signal from HOMO-2 of
CO2. The parameters are given in the text.

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3rd International Conferences and Workshops on Basic and Applied Sciences 2010

We now in position to show the HHG signal of

aligned CO2. To this end, an ensemble of CO2
molecules was aligned by using pump pulse of peak
intensity 0.757 1014 W/cm2 and pulse duration 60
fs. The HHG signal then was generated by using
probe pulse of peak intensity 1.71014 W/cm2,
mean wavelength = 800 nm, and pulse duration
60 fs. We choose the initial temperature to be 200
K, which is a typical temperature in the experiment.
The calculated HHG signal for 19th and 15th orders
are given in Fig. 6. The calculated signal shows a
revival at quarter, half, and full period with Trev =
42.7 ps, which is in according with the
experimental data [6, 8, 9]. The value of Trev is also
consistent with the rotational constant of CO2. In
addition to above revival, the revival at (1/8) Trev is
also observed, as a fingerprint of contribution of
HOMO. This eight revival is also seen in the
experiment [6, 8, 9].

ISBN: 978-979-19096-1-7

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Figure 6: The calculated HHG signal for H19

and H15. The parameters are given in the text.
4

Conclusions

To conclude, we have derived the analytical form

HHG signal of aligned CO2, by taking in account
the contribution of HOMO, HOMO-1, and HOMO2. The calculated HHG signal obtained by using the
formula well agree with the experimental data. The
model also clearly predict that the inverted phase
modulation on HHG signal is due mainly to the
contribution of it HOMO-1.

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