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PRL 109, 123001 (2012) PHYSICAL REVIEW LETTERS 21 SEPTEMBER 2012

Molecular-Frame 3D Photoelectron Momentum Distributions by Tomographic Reconstruction

Jochen Maurer,1 Darko Dimitrovski,2 Lauge Christensen,3 Lars Bojer Madsen,2,* and Henrik Stapelfeldt1,4,†
1
Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark
2
Department of Physics and Astronomy, Lundbeck Foundation Theoretical Center for Quantum Systems Research, Aarhus University,
8000 Aarhus C, Denmark
3
Department of Physics and Astronomy, Aarhus University, 8000 Aarhus C, Denmark
4
Interdisciplinary Nanoscience Center (iNANO), Aarhus University, 8000 Aarhus C, Denmark
(Received 11 June 2012; published 18 September 2012)
Naphthalene molecules are fixed in space by a laser field and rotated, in 2
steps, over 180
. For each
orientation, they are ionized by an intense, circularly polarized femtosecond laser pulse, and the 2D
projection of the photoelectron momentum distribution is recorded. The molecular-frame 3D momentum
distribution is obtained by tomographic reconstruction from all 90 projections. It reveals an anisotropic
electron distribution, angularly shifted in the polarization plane, that is not accessible by the 2D
momentum images. Our theoretical analysis shows that the magnitude of the angular shift is very
sensitive to the exact form of the laser-modified molecular potential.

DOI: 10.1103/PhysRevLett.109.123001 PACS numbers: 33.60.+q, 33.80.Eh, 33.80.Rv, 42.50.Hz

An important tool in medical imaging is x-ray computed
tomography, enabling three-dimensional (3D) imaging of
the inside of the human body. The basic idea of computed
tomography is to record two-dimensional (2D) x-ray im-
ages for a large number of irradiation angles of an object
and retrieve its 3D spatial distribution by tomographic
reconstruction from all 2D images. Recently, the principle
of tomography made its entry into photoelectron imaging
with the aim of determining the 3D photoelectron momen-
tum distribution (PMD) stemming from ionization of
atoms or molecules by laser pulses. For atoms, it was
demonstrated that the 3D PMD could be retrieved from a
sufficiently large set of projections on a 2D imaging
detector [1,2]. The different projections were obtained by
rotating the polarization state of the ionizing laser pulse
with respect to the detector because the emission direction
of the photoelectrons from spherically symmetric atoms
is uniquely determined by the polarization state.
Tomographic reconstruction was extended to randomly
oriented molecules [3], but this only gives the 3D PMD
in the laboratory frame. To extract maximum information
from PMDs, it is necessary that they are measured with
respect to the molecular frame (MF). Exploiting tomogra-
phy to retrieve a MF 3D PMD requires, therefore, that the
molecular-frame rather than the laboratory-frame PMD is
rotated with respect to the detector. As demonstrated in the
present Letter, this can be obtained by sharply aligning
molecules and rotating them over 180
.
The motivation for our studies is that the MF 3D PMD is
the most differential quantity from which more commonly
used observables, like the kinetic energy distribution of the
photoelectrons [4,5], can be derived. One established ex-
perimental approach is photoelectron-ion coincidence
techniques. The detector type, typically employed, pro-
vides 3D PMDs [6], and the molecular frame is accessed
by measuring the spatial orientation of each molecule from
which electrons are being recorded. This is possible if the
ionization event leads to fragmentation in a way that the
emission direction of recoiling ions, detected in coinci-
dence with the photoelectrons, identifies the molecular
frame at the instant of ionization. Photoelectron-ion coin-
cidence techniques have enabled a range of seminal studies
on small, typically linear or symmetric top molecules
where only a single molecular axis needs to be determined
[7–11]. For more complex molecules, the unlikely exis-
tence of a fragmentation pattern that uniquely identifies the
molecular orientation makes coincidence methods a non-
viable route to retrieve MF PMDs [12]. Furthermore, often
ionization does not lead to fragmentation which, obviously,
excludes the application of coincidence methods.
An alternative and more general approach to access the
molecular frame is to fix the molecular orientation prior to
the ionization event. Here, we show that the ability, based
on moderately intense, nonresonant laser pulses [15], to
confine the spatial orientation of molecules and controlla-
bly rotate them combined with tomographic reconstruction
opens a new approach to measurements of MF 3D PMDs.
We use this new ability to determine the MF 3D PMDs
created by strong field ionization with intense circularly
polarized laser pulses and show that it is a sensitive probe
of the asymptotic laser-modified molecular potential.
The principle of the experiment is illustrated in Fig. 1
(see Ref. [16]). A cold molecular beam of naphthalene
molecules (rotational temperature 1 K) enters a velocity
map imaging (VMI) spectrometer where it is crossed at
90
by two pulsed laser beams. The first pulse (YAG pulse:

¼ 1064 nm, FWHM ¼ 10 ns, I0 ¼ 8  1011 W=cm2 ) is
elliptically polarized, shown by the red ellipse in Fig. 1,
with an intensity ratio of 3:1 between the major and the
minor polarization axes. It adiabatically 3D aligns the long

0031-9007=12=109(12)=123001(5) 123001-1 Ó 2012 American Physical Society


PRL 109, 123001 (2012) PHYSICAL REVIEW LETTERS
FIG. 1 (color online). (a) Schematic of the experimental setup
showing a naphthalene molecule aligned by the elliptically
polarized YAG pulse (red ellipse) and ionized by the circularly
polarized probe pulse (red spiral). The VMI spectrometer
projects the photoelectron momentum distribution onto the de-
tector, and the 2D electron images are recorded for 90 align-
ments of the molecule over a 180
interval obtained by rotating
the YAG polarization ellipse in steps of 2
around the x axis.
Examples of electron images for the major axis of the ellipse
parallel to (vertical) and perpendicular to (horizontal) the detec-
tor are shown in (b) and (c), respectively.
molecular axis (y0 axis) along the major polarization axis
and the short molecular axis (z0 axis) along the minor
polarization axis (Fig. 1). The degree of alignment is not
quantitatively characterized, but due to the high polariz-
ability (anisotropy) of naphthalene, the alignment is ex-
pected to be high and similar to that of 2,6
difluoroiodobenzene [17]. The second pulse (probe pulse:
800 nm, 30 fs, 9  1013 W=cm2 ) is circularly polarized. Its
electric field vector is given by FðtÞ ¼ pFffiffi20 cos2 ðt=Þ 
½cosð!tÞez  sinð!tÞey , with the plus sign referring to a
left-circularly polarized (LCP) and the minus sign to a
right-circularly polarized (RCP) pulse, ! corresponding
to the wavelength of 800 nm, and  the pulse duration. The
probe pulse is synchronized to the peak of the YAG pulse,
where the molecular alignment is strongest, and it singly
ionizes the naphthalene molecules. The photoelectrons are
projected onto a 2D detector, and the images are captured
by a CCD camera.
To provide the complete set of projections of the PMD,
needed for tomographic reconstruction, electron images
were recorded for 90 equally spaced alignments of the
molecules in a 180
interval obtained by rotating the
polarization ellipse over 180
in steps of 2
. This step
size is sufficiently fine to avoid any significant artifacts
in the reconstruction. The circular polarization state of the
probe pulse was kept fixed. Examples of two electron
images are depicted in Fig. 1, one with the long molecular
axis parallel (b) and one with the axis perpendicular (c) to
the detector. The images show that the electrons are ejected
in a stripe parallel to the polarization plane of the probe
pulse with a pronounced suppression for px0 ¼ 0. The
123001-2
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21 SEPTEMBER 2012
interpretation of the images was given recently [18,19],
notably that the suppression results from the nodal plane
that coincides with the molecular plane, in the orbitals
from where electrons are detached. This can be understood
qualitatively by noting that ionization with a field in the
nodal plane is forbidden because there is no electronic
population in the nodal plane. For naphthalene, the highest
occupied orbital has a structure similar to the atomic fxyz
orbital, possessing three nodal planes.
The tomographic reconstruction was performed for each
2D slice along the laser beam propagation direction by the
filtered backprojection method for parallel projections, a
fast, efficient, and widely used method for tomographic
reconstruction [20,21]. During the reconstruction, the fil-
tering step was performed with a Hann-type filter in the
frequency space with a cutoff frequency of half of the full
frequency range. Furthermore, the reconstructed data were
smoothened with a spatial Gaussian filter after the recon-
struction. Both methods are commonly used in the case of
reconstruction of low statistics data [22–24]. The close
similarity of the unprocessed reconstructed data with the
symmetrized and filtered input data confirmed that no
information was lost and no artifacts were introduced
during the reconstruction procedure.
Figure 2 represents the outcome of the reconstruction for
a RCP probe pulse by showing an isosurface of the mo-
mentum distribution, i.e., points in momentum space
where the MF 3D PMD, Pðpx0 ; py0 ; pz0 Þ, attains a constant
value. The isosurface resembles a modulated torus with a
groove centered at px0 ¼ 0. This is the structure originating
from suppression of electron emission in orbital nodal
planes, see also [Figs. 1(b) and 1(c)]. Second, a hollow
out in the center of the surface along the x0 axis is observed.
FIG. 2 (color online). Tomographic reconstruction of the mo-
lecular frame 3D photoelectron momentum distribution, repre-
sented by an isosurface, when naphthalene molecules are ionized
by a RCP probe pulse. The momenta at the isosurface value of
0.035 are given in atomic units (a.u.). The result obtained with a
LCP probe pulse is almost identical except that the angular shift
of the isosurface in the field polarization plane y0 and z0 is in the
opposite direction.

PRL 109, 123001 (2012) PHYSICAL REVIEW LETTERS
Although this structure also manifests itself in the 2D
images as a formation of a waist along the horizontal center
line, its true magnitude is only revealed in the 3D distri-
butions. Third, the peak emission direction does not coin-
cide with either the long (y0 ) or the short (z0 ) molecular
axis. This characteristic cannot be seen in the 2D electron
images. In the following, we focus on this angular shift of
the MF 3D PMD and analyze its origin and magnitude.
The angular shift of PMDs, associated with ionization
by intense laser pulses, has been addressed in several
previous works [25–29]. The main emphasis has been on
ionization of atoms with an elliptically polarized laser
pulse [25–27]. Here, the electron is released when the laser
field is strongest, i.e., pointing along the major polarization
axis, and the shift results from the subsequent distortion of
the laser driven electron trajectory by the field from the
cation. In the current work, the anisotropy in the electron
emission is not due to any anisotropy in the polarization
state of the ionizing field (since it is circularly polarized),
but rather to the dependence of the ionization yield on the
orientation of the field vector with respect to the mole-
cule—a phenomenon that is general for most anisotropic
molecules [30].
The analysis is based on determining the PMD in the
polarization plane, i.e., the y; z plane which, for (perfectly)
aligned molecules coincides with the molecular y0 ,
z0 -plane. In particular, we obtain the PMD in and parallel
to the molecular plane for the five px0 intervals, defined in
the caption to Fig. 3, by projecting the 3D PMD pertaining
to these intervals onto the polarization plane. This is an
example of observables that can only be accessed due to
the availability of the 3D PMD. The results for a RCP
probe pulse, displayed in Fig. 3, reveal anisotropic PMDs,
each with a peak emission direction in between the long
and the short molecular axis despite the circular symmetry
FIG. 3 (color online). Projections of the 3D momentum
distribution onto the polarization plane from 3D aligned naph-
thalene molecules ionized with a RCP probe pulse. The five
different projections correspond to five different px0 intervals:
(a) 0.117–0.194 a.u., (b) 0.194–0.272 a.u., (c) 0.272–0.350 a.u.,
(d) 0.350–0.427 a.u., (e) 0.427–0.583 a.u. (f) The geometry of the
projections with respect to the molecule and the probe pulse
polarization. The probe pulse propagates into the paper.
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exhibited by the circular polarization state of the ionizing
laser in this plane. It is seen that the angular shift, defined
as the counterclockwise (viewed from the side of the
incoming pulse in the -pz0 -py0 plane) offset of the PMDs
from the short molecular axis, is largest for the px0 interval
containing the smallest px0 values and that it gradually
decreases as the values in the px0 interval increase [31]. It
is also seen that the maximum in the radial distribution
shifts to larger values as the px0 interval increases, reflect-
ing the fact that high momenta electrons are produced from
focal volume regions where the probe pulse intensity is
high. We identify the maximum in the radial momentum
distribution for each px0 interval—either directly from the
data points or from an asymmetric Gaussian model fit [32]
and assign an effective probe pulse intensity using the
calculated dependence of the maximum radial momentum
as a function of probe pulse intensity [34]. Hereby we are
able to plot the angular shift versus the effective probe
intensity. The results (the numerical value of the angular
shifts) for both helicities of the probe pulse are shown in
Fig. 4.
To qualitatively understand the origin of the angular
shift, we note that during an optical cycle the electric field
vector of the probe pulse, FðtÞ, completes a full rotation in
the plane of the naphthalene molecules. For naphthalene,
in the tunneling limit, ionization occurs most efficiently for
the direction of the field where the ionization potential,
Stark shifted by the polarizability interaction with FðtÞ, is
lowest [18,35–37]. This occurs when FðtÞ points along the
long molecular axis where the polarizability difference
between the neutral molecule and its cation is largest.
Upon release, the electron is influenced by the remainder
of FðtÞ which would cause the electron to be emitted 90

( 90
) away from the long molecular axis, i.e., along the
50
LCP (Asymmetric Gauss)
RCP (Asymmetric Gauss)
40 LCP (Direct Maximum)
RCP (Direct Maximum)
|angle| [degrees]
30
20
10
0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
14 2
Intensity [10 W/cm ]
FIG. 4. Numerical values of the experimental (symbols) and
theoretical (curves) angular shifts of the electron momentum
distribution in the polarization plane as a function of probe pulse
intensity for naphthalene. Full curve: Perfectly aligned mole-
cules, full ionic potential; Dashed curve: Perfectly aligned, only
Coulomb potential. Dotted curve: Nonperfectly aligned mole-
cules (see text), full ionic potential. The experimental points are
plotted for both LCP and RCP probe pulses. See text for details.

PRL 109, 123001 (2012) PHYSICAL REVIEW LETTERS
short molecular axis for a LCP (RCP) probe pulse. The
angular shift results from the fact that the electron is, in
addition to FðtÞ, also influenced by the Coulomb field of
the molecular cation and the electric field from the dipole
moment induced in the cation by the probe pulse.
Theoretically, we analyze the angular shift of the PMD
using a semiclassical two-step model, where the first step is
tunneling and the second step involves propagation of
classical trajectories from the tunnel exit point [38,39].
The probability of tunneling depends on the Stark-shifted
ionization potential Ip ðFÞ ¼ Ip ð0Þ þ 12 FT ðN   I ÞF,
where F is the instantaneous electric field vector and N
and I are the static polarizability tensors of the neutral
and the cation, respectively, with components taken from
Ref. [40]. The naphthalene potential is modeled as
Z ðI FÞ  r
VðrÞ ¼   ; (1)
r r3
for not too small distances [36].
The angular shift of the PMD (Fig. 4) is calculated for
both perfectly and imperfectly aligned molecules and by
taking into account only the most probable classical tra-
jectory—the trajectory launched at the peak of the pulse
when F points along the long molecular axis. The angular
shift calculated as a function of the probe pulse intensity is
shown in Fig. 4 together with the experimental results. The
experimental data are not compatible with the calculation
that only includes the Coulomb field from the cation
(dashed curve in Fig. 4). Instead they scatter around the
curve calculated with the full ionic potential included (full
curve in Fig. 4). The reason for the larger angular shift
when only the Coulomb potential is included is the smaller
tunnel exit point as compared to the exit point when the full
potential of Eq. (1) is present. Moreover, the induced
dipole term ‘‘shields’’ the electron from the influence of
the Coulomb potential (attractive force) in the initial stages
of propagation in the continuum (immediately after tun-
neling). The induced dipole moment, i.e., the laser modi-
fication to the molecular potential, also explains why the
shift decreases when the probe intensity increases. As the
intensity is increased the induced dipole moment becomes
larger and so does the shielding of the Coulomb field. For
completeness, we also calculated the angular shift for
molecules with an alignment distribution that simulates
the one expected in the experiment [41]. The results (dot-
ted curve in Fig. 4) show angular shifts only slightly
smaller than those for perfectly aligned molecules and
are, thus, still in good agreement with the experimental
findings.
The results presented here show that the magnitude of
the angular shift of the PMD is determined by the cationic
molecular potential that acts on the departing electron. As
such, measurements of the angular shift of photoelectrons
created by ionization of molecules with an intense circu-
larly polarized (or elliptically polarized) femtosecond
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probe pulse may provide a method for time-resolved prob-
ing of changes in the molecular potential induced by a
pump pulse.
Our method to retrieve the MF 3D PMD will be gen-
erally applicable to a broad range of nonpolar molecules
independent of the ionization process leading to fragmen-
tation or not. The resolution in the reconstructed PMDs can
be increased by employing methods to further sharpening
the 3D molecular alignment [19]. An interesting challenge
is the extension to polar molecules where a uniform ori-
entation (head-versus-tail asymmetry) is required for the
3D tomographic reconstruction for all alignment positions
of the molecules. This may be achieved by adjusting the
static electric field in the VMI spectrometer such that the
component along the permanent dipole moment axis re-
mains constant as the molecules are rotated.
The work was supported by the Danish Council for
Independent Research (Natural Sciences), The Lundbeck
Foundation, the Carlsberg Foundation, the European
Marie Curie Initial Training Network Grant No. CA-
ITN-214962-FASTQUAST, and ERC-StG (Project
No. 277767-TDMET). We acknowledge helpful discus-
sions with Matthias Wollenhaupt and Thomas Baumert.
*bojer@phys.au.dk
†
henriks@chem.au.dk
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