Structural Dynamics

High-harmonic spectroscopy of transient two-center interference

calculated with time-dependent density-functional theory
François Mauger,
1, a) Paul M. Abanador,
1
Timothy D. Scarborough,
2
Timothy T. Gorman,
2
Pierre Agostini,
2

2 3 1 1
Louis F. DiMauro, Kenneth Lopata, Kenneth J. Schafer, and Mette B. Gaarde
1) Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana 70803,
USA
2) Department of Physics, The Ohio State University, Columbus, Ohio 43210, USA
3) Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803,
USA
(Dated: 20 June 2019)
We demonstrate high-harmonic spectroscopy in many-electron molecules using time-dependent density-functional the-
ory. We show that a weak attosecond-pulse-train ionization seed properly synchronized to the strong driving mid-
infrared laser field can produce experimentally-relevant high-harmonic generation (HHG) signals from which we ex-
tract both the spectral amplitude and target-specific phase (group delay). We also show that further processing of the
HHG signal can be used to achieve molecular-frame resolution, i.e., to resolve the contributions from rescattering on
different sides of an oriented molecule. In this framework, we investigate transient two-center interference in CO2 and
OCS, and how sub-cycle polarization effects shape oriented/aligned angle-resolved spectra.

I. INTRODUCTION microscopic-scale field emitted by individual molecules,

and the measured macroscopic response24–26 . The single-
High-harmonic spectroscopy (HHS) is based on the idea molecule response consists of multiple so-called quantum-
of using the spectral properties of high-harmonic genera- orbit contributions that give rise to broad, unresolved spec-
tion (HHG) signals to coherently probe atomic or molecu- tral features27 . The macroscopic response is dominated by
lar systems1–3 . For instance, it has been used to recover phase-matched radiation originating in the shortest quantum-
internuclear distances4–6 or image molecular wave-functions orbit contribution, which is reasonably well resolved in the

20 March 2024 08:11:30

with tomographic reconstruction algorithms7–10 . Conceptu- temporal, spectral, and spatial domains. HHS is built upon the
ally, HHS also provides a built-in temporal dimension with intrinsic coherence of HHG spectra, where the same electron
sub-femtosecond resolution. This is based on the fact that that was first ionized returns and probes its parent cation28,29 .
HHG emission is naturally synchronized with the laser field Meaningful information about the target’s structure and dy-
and different harmonics are mapped to sub-laser-cycle emis- namics can therefore only be extracted from harmonic emis-
sion times11,12 . As an example, HHS has recently been used sion originating in a single quantum orbit contribution. Nu-
to measure charge migration in molecules13–15 . A complete merically, macroscopic effects can, in principle, be accounted
characterization of increasingly complex molecular struc- for by incorporating the single-molecule response into a wave-
tures and dynamics via HHS techniques will require multi- equation solver throughout the generating gas medium, as is
dimensional analyses and access to the full information con- routinely done for single-active-electron systems30,31 . How-
tained in these HHG signals, and the ability to measure both ever, the individual computation cost of one TDDFT-HHG
amplitude and phase information16,17 of (preferably) oriented calculation still makes this approach prohibitive for more
molecules18 will have to become standard. complex systems.
Theoretically and numerically, the challenges of treating
In this paper we use TDDFT to explore HHS in two linear
a correlated many-electron system responding to a strong
molecules at mid-infrared (MIR) wavelengths: the symmetric
laser field are tremendous and cannot be done without sig-
(non-polar) CO2 and the asymmetric (polar) OCS molecules.
nificant approximations. In this context, time-dependent
We calculate the harmonic spectral amplitude and phase in
density-functional theory (TDDFT) offers a scalable compu-
the vicinity of a two-center interference (TCI) minimum in
tational framework for many-active-electron molecules inter-
each molecule, as a function of the relative angle between the
acting with the laser. In spite of some known drawbacks19
molecular axis and the linearly polarized laser field – see17
(most prominently that an exact exchange-correlation func-
for more details on TCI and direct comparisons to experimen-
tional is not known), TDDFT has recently been validated
tal results. We show that we can reliably select the contri-
against other calculations or experimental results in a number
bution from the short quantum orbits to the harmonic spec-
of studies related to ultrafast and strong-field processes, such
trum by combining the MIR laser field with an attosecond
as high-harmonic spectroscopy17 , strong-field ionization20–22
pulse train (APT) that coincides with the ionization time of
or charge migration23 .
the short quantum orbit in each half-cycle of the field. As
A difficulty when calculating HHG spectra using first-
demonstrated in helium atoms32,33 , this ionization seed leads
principles methods is the stark difference between the
to a harmonic spectrum dominated by the short-orbit contri-
bution. We show that this yields TDDFT-calculated spectral
amplitudes and phases which are sufficiently well-resolved
a) Electronic mail: fmauger@lsu.edu to recognize the characteristic angle-dependence of the TCI
Structural Dynamics 2

minimum17 . We also find that by selecting the short-quantum-

orbit contribution from a single laser half-cycle, we naturally
obtain molecular-frame information about the HHG process
since we can discriminate between rescattering from the two
sides of an asymmetric molecules. As an example, we show
that the harmonic spectrum is substantially different when the
returning electron rescatters on the O side relative to the S
side of OCS, and we interpret this in terms of the instanta-
neous field-induced redistribution of the electron density in
the molecular core. In particular, we show that when rescat-
tering on the electron-heavy S side, the laser field rebalances
the distribution of charge density so that the two centers are
more even than in the undressed molecules, and this leads to
FIG. 1. Illustration of the laser fields used to select short-quantum-
a clear TCI minimum in the harmonic spectrum.
orbit contributions to harmonic spectra in TDDFT computations.
The paper is organized as follows. Section II describes The weak ionization-seed APT is synchronized with the strong driv-
our theoretical and numerical approach, detailing the TDDFT ing MIR field. The delay ∆ between the APT and MIR is selected
and ionization-seed numerical methods as well as the HHS to get the best enhancement of short-contributions only (see sec-
analysis. In this section we also show some technical re- tion II C).
sults demonstrating the efficacy of the ionization seed. Sec-
tion III presents angularly resolved HHS investigations in the
molecular-frame picture as discussed above, showing the dif- as compared to experimental values of 13.77 eV and 11.17 eV,
ference between rescattering from the S or O sides of the OCS respectively44 .
molecule, as well as their interplay when forming aligned- As discussed in the introduction, the laser field is composed
only spectra. Then, in Section IV, we interpret the observed of a strong driving MIR plus a weak ionization-seed APT, syn-
spectral features in terms of transient TCI processes, where chronized with the MIR – see Fig. 1. For the MIR, we use a
two localized density components of the target’s electronic linearly polarized laser field with a wavelength of 1500 nm
structure lead to harmonic emission which interferes destruc- and an intensity of 60 TW/cm2 , which leads to a harmonic

20 March 2024 08:11:30

tively. We show that such TCI features provide a good land- plateau that extends to 50-60 eV in the two molecules. This
mark to probe sub-cycle density dynamics in the compound. means that the TCI minimum is within the plateau range for
Finally, section V concludes our analysis and discusses possi- angles up to about 45◦ . The field envelope is ramped up with
ble application perspectives for the study of charge migration a sin2 shape during the first two cycles of the pulse, and then
in molecular targets. kept constant. The harmonic spectrum is calculated from the
Unless otherwise stated, atomic units are used throughout constant-intensity part of the pulse, as described in detail in
the paper. We also define the angle θ between the oriented section II B.
molecular axis of CO2 /OCS and the laser-field polarization The APT ionization seed is composed of 5 MIR-odd-
direction. harmonics with energies close to the ionization threshold, with
harmonics 9 through 17 in CO2 , and 7 through 15 in OCS. The
APT intensity and sub-cycle delay relative to the MIR elec-
II. METHODS tric field are chosen such that the HHG yield is dominated by
the contribution from electrons that are one-photon-ionized by
A. Time-dependent density-functional theory simulations the seed32 : The envelope of the APT is matched to that of the
MIR and its peak intensity is either 2% (CO2 ) or 1% (OCS)
For the TDDFT computations, we use a local-density ap- of the MIR. The timing of the APT ionization seed is chosen
proximation (LDA) exchange-correlation potential34–37 with such that it coincides with the time during the MIR cycle at
average-density self-interaction correction38 (ADSIC), as im- which the short orbits are initiated. This means that the APT
plemented in OCTOPUS39,40 . The self-interaction correction should be centered shortly after the peaks of the MIR field, as
ensures that the asymptotic (long-range) behavior of the po- illustrated in Fig. 1. For the calculations shown in this paper,
tential is Coulombic, as is necessary for proper HHG spec- we have used delays ∆ between 0.06 and 0.08 MIR cycles.
tra41–43 . The Kohn-Sham equations are solved on a Cartesian More details about the timing of the APT are provided in sec-
grid with a spacing of 0.4 a.u. in all directions and with the tion II C.
molecule centered in the simulation box. The dimensions of
the box are 195 a.u. in the direction parallel to the laser polar-
ization, and 30 a.u. in the perpendicular directions. The tem- B. High-harmonic spectroscopy

poral step for all time-dependent computations is 0.05 a.u. and

we have checked the convergence of reported spectra for all Spectral yield: The harmonic spectral properties are cal-
computational parameters. For reference, we find numerical culated from the TDDFT time-dependent dipole acceleration
ionization potentials (energy of the highest-occupied molecu- signal a (t, θ ), which has components both parallel and per-
lar orbital) of I p =14.55 eV for CO2 and I p =11.67 eV for OCS, pendicular to the laser polarization. The spectral intensity is
Structural Dynamics 3

the incoherent sum of the parallel and perpendicular contribu-

tions:
2
|HHG (ν , θ )|2 = F [W (t)a∥ (t, θ )] + |F [W (t)a⊥ (t, θ )]|2 ,
(1)
where ν is the frequency, F denotes the Fourier transform
and W (t) is a time-selection window, which is shaped like
cos4 . W (t) allows us to select the time-dependent response
from one or multiple half-cycles of the laser field. Selecting
a single half-laser-cycle allows us to distinguish the harmonic
spectrum by the orientation of an asymmetric molecule, i.e.,
we expect to see a difference between molecules of opposite
orientations (see section III).
Fig. 2(a-b) shows the spectral yield in the symmetric
molecule CO2 , for alignment angles of (a) θ = 0◦ and (b)
θ = 15◦ , generated by the MIR alone (lower red curves) and
by the MIR+APT (upper blue curves). The thick and thin
curves, in each case, correspond to using two different win- FIG. 2. HHS analysis of TDDFT simulations in CO2 for 0◦ (left
dow functions, which select either a single half-cycle (from panels) and 15◦ (right) alignment. Panels (a-b) compare the spectral
intensity of Eq. (1) with the MIR-only and APT-ionization-seed (see
2.05 to 2.55 cycles, thick lines) or four half-cycles (from 2.05
labels). Single sets of short orbits (thick curves) are selected with
to 4.05 cycles, thin lines), respectively, of the time-dependent a window W (t) spanning 2.05-to-2.55 laser-cycles, and full spectra
response. The figure demonstrates several important points: (thin) use a window between 2.05 and 4.05 cycles. Panels (c-d) show
First, at 0◦ , the TCI is clearly visible with a local minimum the single-short-orbit target-specific group delay of Eq. (4) using a
in the spectral intensity around 45 eV (vertical dotted line). one- (dashed curves) and two-dimensional (solid) reference. The
Physically, the TCI minimum can be understood as a destruc- driving MIR has a 1500-nm wavelength and a 60-TW/cm2 intensity;
tive interference between the scattering contributions from the the parameters for the APT seed are specified in section II A. The
two ends of the molecule45–47 (see section IV). In this picture, vertical dotted line in (a,c) labels 45 eV.
the energy location of the minimum is related to the effective

20 March 2024 08:11:30

distance between the two centers seen by the (re)scattering
electron48,49 . As such, the position for the TCI is expected to the plateau, which combines the effects of the APT seed and
shift to higher energies as θ is increased away from parallel the fact that a single set of recolliding orbits has been effec-
orientation. This angle dependence has been confirmed exper- tively generated by the MIR thus far. Finally, the TCI min-
imentally for CO2 , although it is not as fast as predicted by a imum is much clearer in the APT-seeded spectra; at 15◦ the
plane-wave rescattering electronic-wave-function17 . minimum is not even visible in the MIR-alone spectrum, and
Second, Fig. 2(a-b) illustrates the effect of the APT on the at 0◦ it is weaker than in the seeded spectrum.
harmonic spectrum: (i) for the seed intensity we consider here, Fig. 3 further illustrates the effect of the ionization seed. It
the APT clearly dominates the ionization step and leads to an shows the time-frequency representation (spectrogram) of the
HHG spectrum which is several orders of magnitude stronger harmonic emission in the first three half-cycles of constant
than that of the MIR alone, (ii) the APT does not substan- MIR intensity, (a) without and (b) with the APT seed. The
tially influence the position of the cutoff energy, and (iii) the spectrogram is computed from Eq. (1), using a cos4 sliding
APT-initiated spectrum is much cleaner than the MIR-alone window with 1-fs duration. Again, Fig. 3(a) shows how, in
spectrum, with odd harmonics clearly separated from each the absence of the APT, both the short and longer quantum
other (thin curves). All of these points are consistent with orbits contribute to the HHS signal and the long orbit domi-
the findings for helium atoms in32 , and can be understood nates. The TCI minimum is only weakly visible in the short-
from the three-step picture of HHG in which the spectrum is orbit branch. In contrast, the APT-seeded spectrogram in (b)
the product of an ionization probability, a rescattering wave is strongly dominated by the short-orbit contribution, which
packet, and a recombination dipole moment50–52 . The APT has a clear TCI minimum. It is also worth noting that in the
can clearly enhance the ionization step by substituting tunnel APT-seeded case, in the low-energy part, there is a substan-
ionization with one-photon ionization, and its timing is such tial amount of emission which does not seem to follow any
that it predominantly launches electrons on the short quan- particular orbit contribution. This is most likely caused by
tum orbit (see more details below). However, it has a neg- electrons from lower-lying orbitals that can be ionized by the
ligible influence on the continuum dynamics, which is con- broad-bandwidth APT, and then contribute to the continuum
trolled by the MIR field, and the recombination probability, and rescattering dynamics. We will come back to this issue in
which is specific to the molecule. In addition, the use of the section II C.
short time-selection window (thick curves) further eliminates Fig. 3 also illustrates why the time-selection window in
interferences between dynamics initiated in consecutive half- combination with the APT seed works well to select a sin-
cycles and isolates the contribution from a single half-cycle, gle set of short quantum orbits: each set of ionization-seed-
while not changing the overall spectral shape. Typically, the enhanced short orbits are temporally separated, roughly be-
cleanest signal is obtained during the first half laser cycle of tween successive zeros of the laser electric field. We also note
Structural Dynamics 4

where aref (t) is the acceleration signal from the refer-

ence atom, subjected to the same MIR+APT laser field,
and calculated by numerical solution of the time-dependent
Schrödinger equation. At the very least, the companion-atom
normalization provides a common reference to compare fea-
tures in the GD, e.g., as the orientation/alignment angle is var-
ied. Finally, the total GD is obtained by weighting the con-
tributions from the parallel and perpendicular directions with
their respective intensities
[ ]2
F Wa∥ GD∥ + |F [Wa⊥ ]|2 GD⊥
GD = [ ]2 . (4)
F Wa∥ + |F [Wa⊥ ]|2

The weighting above ensures that the results of Eq. (4) are
unchanged by a rotation of the simulation domain with fixed
angle θ .
The CO2 -specific GD for two different alignment angles is
shown in Fig. 2(c,d), for both the MIR-alone (red) and the
MIR+APT (blue) cases. At 0◦ , both the MIR-alone and the
FIG. 3. Spectrograms of TDDFT simulations in CO2 for 0◦ with the
(a) MIR only and (b) APT-ionization seed. On each panel, dashed APT-seeded GDs show a minimum at the position of the TCI
curves label strong-field-approximation (a) long- and (b) short-orbit minimum. One would expect to see such a minimum (or max-
contributions27 . The horizontal dotted line labels 45 eV. Parameters imum) in the GD signal around the TCI as it corresponds to a
are the same as in Fig. 2 (a) [see also section II A]. phase shift of near ±π associated with the destructive interfer-
ence seen in the amplitude. For the 15◦ case, the MIR alone
GD, again, shows no discernible feature near the minimum.
that the time-frequency map has half-cycle periodicity, which Fig. 2(c,d) also shows a comparison of results using a one-
again supports the idea that the ionization seed enhances the (dashed curves) and two-dimensional (continuous) reference

20 March 2024 08:11:30

short orbit signal without triggering longer-time-scale pro- atom in Eq. (4). The close similarity between the two makes
cesses. us confident in our method for extracting target-specific group
Group delay: We also extract phase information from the delays.
TDDFT calculations and calculate the target-specific group Compared to the amplitude part of HHG signals, meaning-
delay (GD). Experimentally, the GD is extracted from inter- ful target-specific GDs are much more challenging to extract.
ferometric measurements53,54 and it is related to the spectral Part of this is due to the fact that the phase typically carries
phase by a derivative. The target-specific GD is the contribu- most of the information (for example, the phase is the basis
tion to the GD from the rescattering alone, and it is calculated for tomographic reconstruction algorithms56 ). Additionally,
after normalizing the acceleration spectrum by that of a com- the generic part of the GD (the attochirp) usually dominates
panion atom with an identical I p 17,55 . This normalization can over the target-specific part that is of interest to us. Finally,
be understood in the framework of the three-step model, and despite our best efforts to minimize its effects, the addition of
formalized in the quantitative rescattering (QRS) approach, the APT field does contribute to the overall HHG phase, and
where HHG signals are factorized in the frequency (ν ) do- thus the GD, possibly including at the ionization step. The
main50–52 : reference normalization of Eq. (3) plays an important role in
removing (some of) these systematic contributions. Because
the reference is computed with an identical total field, includ-
HHG (ν ; θ ) = Ion. (θ ) × Prop. (ν ) × Scatt. (ν ; θ ) . (2)
ing the APT, we expect the effects of the ionization seed to be
mitigated in the target-specific GD.
The three pieces correspond to the contributions from the
The limitations of target-specific group delay extractions
angle-dependent ionization yield (Ion.), a generic electron
are most visible in the low-energy part of the spectrum,
wave packet associated with the laser-driven propagation of
roughly below 35 eV in Fig. 2 (c,d), where the extracted
the ionized electron (Prop.), and the target-specific and angle-
GD oscillates rapidly and is unreliable. This could be caused
dependent (re)scattering (Scatt.). In this framework, a one-
by interference with lower-lying orbital contributions that are
electron spherically-symmetric atom with the same I p would
made accessible by the broad-band APT. Note also that lower
give rise to the same generic wave packet with a nearly flat
frequencies typically span longer times (longer period) and
scattering phase, and can therefore be used as a reference.
are therefore more prone to interference or noise. Similarly,
The target-specific group delay of the molecule can then be
in the cut-off region beyond about 60 eV in the figure, the
calculated as:
GD becomes unreliable because the amplitude vanishes and
( [ ] ) there is no signal to extract the phase information from. On
∂ F Wa∥/⊥ (θ ) (ν ) the other hand, the close similarity of the results using one-
GD∥/⊥ (θ ; ν ) ≈ − Arg , (3)
∂ν F [Waref ] (ν ) (dashed curves) and two-dimensional (continuous) references
Structural Dynamics 5

FIG. 5. Illustration of molecular-frame analysis provided by half-

laser-cycle-resolved HHS. By considering the short orbit contribu-
tions from individual half-cycles, we resolve the individual contri-
butions to HHS spectra from ionization and recollision from the S
(upward red arrow) and O (downward blue) sides of OCS.

D. Aligned signal
FIG. 4. Comparison of the (a) spectral intensity of Eq. (1) and (b)
target-specific group delay of Eq. (4) with varying APT-MIR timing
– see legend and Fig. 1 for the definition of ∆. Here we compare
For asymmetric targets like OCS, the angle θ is defined
results in CO2 at 0◦ alignment from the first set of short orbits in between the oriented molecular and laser polarization axes.
the plateau. Other parameters are the same as in Fig. 2 (a) [see also As illustrated in Fig. 5, this means discriminating between
section II A]. “head” (here S) and “tail” (O) molecular orientation. Ex-

20 March 2024 08:11:30

perimental measurements, however, may achieve alignment
only, i.e., with a macroscopic mixture of molecules with oppo-
site head-tail orientation. Even in instances where orientation
highlights the robustness our method for extracting target- is achieved experimentally, the degree of orientation is often
specific GDs. While challenging, experimental campaigns very small60–63 . Accordingly, we also compute spectral prop-
have demonstrated the crucial role of the phase information erties of aligned molecules by substituting a coherent average
in completing a full characterization of TCI and other struc- of the acceleration signals in opposite-orientation directions
tural features17,55,57–59 .
aligned a∥/⊥ (θ ) + a∥/⊥ (θ + 180◦ )
a∥/⊥ (θ ) = (5)
2
in Eqs. (1-4). Alternatively, assuming that the APT ionization
C. Timing of APT ionization seed
seed generates a new set of short orbits without longer-time-
scale effects, one may use the time-inversion symmetry of the
We mentioned above that the APT delay should be opti- MIR+APT laser
mized for each system. In Fig. 4 we compare the (a) spectral ( π )
intensity and (b) target-specific GD in CO2 using different a∥/⊥ (t, θ + 180◦ ) = a∥/⊥ t + , θ . (6)
ω
MIR-APT delays (see legend). It shows that, while qualita-
tively similar, the specifics of both signals are influenced by In practice, longer-time-scale effects are never fully sup-
the delay, and the GD is the most sensitive to it. For ∆ = 0.08 pressed, and Eq. (6) is only ever an approximate way to ob-
MIR cycles (blue), the low-energy part of the spectrum is pref- tain the signal from the opposite orientation. The approximate
erentially enhanced leading to a less well-defined cut-off in time-inversion symmetry, however, can be used as a quality
the spectral intensity. On the other hand, the spectrum for test for the ionization seed, as discussed in the following sec-
∆ = 0.04 MIR cycles has the best-defined cut-off but a less tion.
sharp TCI minimum. This suggests that optimal delays have
a slight dependence with the HHG frequency, which is com-
patible with selective sub-cycle enhancement of ionization by III. MOLECULAR-FRAME HARMONIC SPECTROSCOPY

the APT seed. Here, to avoid artefacts associated with chang- WITH TDDFT

ing the delay while other parameters are varied (θ ), we select

a fixed delay that gives the best spectra over all angles. For We next move on to molecular-frame HHS of the asym-
CO2 we find that this best delay corresponds to 0.06 optical metric molecule OCS – see Fig. 5. As discussed above, the
cycles after the MIR peaks (and 0.08 cycles for OCS). selection of a single half-cycle of the time-dependent response
Structural Dynamics 6

half-cycles is switched when the orientation of the molecule

is changed by 180◦ . With the aligned signal, in panel (d), we
recover the expected half-laser-cycle periodicity, and a slight
shift in energy of the TCI minimum.
In Fig. 7, we perform a systematic angle scan and com-
pare the spectral intensities as functions of θ for both (a) CO2
and (b-d) OCS. In panel (a) we clearly see the TCI shift to
higher energies as the alignment is moved away from par-
allel – see the thin black guiding curve. From the oriented
molecular-frame contributions, panels (b-c), we see that while
a TCI minimum is visible in the S-side-scattering compo-
nent around 0◦ , its signal is masked in that of the O-side,
leading to the absence of a TCI in the aligned-response for
small angles [panel (d)]. For aligned OCS the minimum is
only apparent for angles |θ | ≥ 20◦ . More generally, detailed
comparison of the three spectral-intensity maps around the
thin black guiding curve once again highlights the subtle in-
terplay between molecular-frame components in forming the
aligned signal. In Ref.17 , we found good qualitative agree-
ment between TCI measurements in aligned CO2 /OCS and
our TDDFT computations64 .
FIG. 6. Molecular-frame harmonic spectroscopy in OCS. Panel (a)
compares the spectral intensity for oriented molecules with recolli-
To better understand the origin of differences between
sion from the O side (220◦ , blue curve) and S side (40◦ , red), and molecular-frame signals recolliding from opposite sides of a
aligned target as defined by Eq. (5) (black) – see also Fig. 5. For molecule, we turn back to the HHG spectrum factorization
each curve, the corresponding spectrograms are displayed in panels of Eq. (2). The ionization piece (Ion.) does not depend on
(b-d), respectively. The driving MIR has 1500-nm wavelength and the HHG energy and can only account for the overall relative
60-TW/cm2 intensity; the parameters for the APT seed are specified strength of one molecular-frame orientation versus the other.
in section II A. Dotted lines label 36 eV.

20 March 2024 08:11:30

Our finding here that S-side-recollision spectra have higher
overall yield is consistent with recent TDDFT calculations
of orientation-dependent ionization yields22 . The propagation
allows us to compare the individual contributions from recol- piece (Prop.) is generic across atomic and molecular species
liding orbits from the S (upward red arrow) and O (downward and does not contain any alignment/orientation dependence
blue) sides of the compound. The comparison of S- and O- and cannot explain the different behavior of the O-side and S-
scattering sides can therefore be done either by rotating the side spectra. This leaves the scattering component (Scatt.) as
system (θ 7→ θ + 180◦ ) or comparing the results from two the only contribution that can influence the location and depth
consecutive half laser-cycles. of the TCI minimum.
Both of these types of comparisons are illustrated in Fig. 6. The scattering term in Eq. (2) is often described as the field-
First, panel (a) shows the spectral yield from opposite orien- free cross-section52
tations of OCS shown in Fig. 5, as well as that of the aligned ⟨ ⟩
ψb dˆ ψc (ν ; θ ) , (7)
signal. It is clear from the figure that there is a stark difference
between recolliding on the O and S sides: recolliding on the where ψb is the bound-component part of the wave function
S side leads to an overall much larger yield as well as a clear – or an orbital representation in DFT frameworks – and dˆ
TCI minimum near 35 eV, which is absent when recolliding is the dipole/velocity/acceleration operator. ψc represents a
on the O side. The figure also shows the alignment-only signal normalized continuum state with momentum mapped to the
(see section II D). Compared to its two oriented components, HHG emission energy ν and rescattering angle θ . The con-
we see that the OCS aligned spectral intensity does not cor- tinuum piece can be approximated by plane-wave, Coulomb-
respond to the intensity-average between its two orientation corrected, or exact continuum states, with various degrees of
contributions. This is best visible in the energy shift of the accuracy51,52,65–67 . In this field-free case, the difference be-
aligned TCI as compared to 40◦ . It highlights the interplay tween scattering from the S and O sides of the molecule (for
and interference between the two orientations’ signals that re- any angle) is simply a sign-change of the phase of ψc , and
shape – and sometimes even occlude – the molecular-frame therefore also cannot account for the intensity difference be-
TCI49 . tween θ and θ + 180◦ . However, the consideration of the
Second, the difference between the two orientations is also field-free scattering cross section is clearly an approximation
illustrated in the spectrograms shown in Fig. 6(b-c). For each since the laser field is present during the rescattering, as we
orientation, the consecutive half-cycles of the spectrogram discuss in more detail in the remainder of the paper.
display different behaviors, corresponding to the direction of In OCS, independent TDDFT simulations, supported by
the field pointing either toward the O or the S end of the matching ionization measurements in the near-infrared22 ,
molecule at the time of recollision, and the behavior in the two have revealed the importance of transient polarization ef-
Structural Dynamics 7

FIG. 7. Normalized spectral intensities in (a) CO2 and (b-d) OCS – oriented molecular-frame scattering from O and S, and aligned, respectively
– as functions of the angle θ . Note that the colormaps in panels (a,d) and (b-c) span different ranges of intensities. For each compound, the
normalization corresponds to a smoothed incoherent average of the aligned signal and is used to reveal features in and beyond the cutoff. In
each panel, the thin black curve is set to I p + α / |cos θ |β , where I p is the target’s ionization potential, as a visual guide for the TCI location17 .
For CO2 (resp. OCS) we set α = 44 eV − I p (resp. α = 33 eV − I p ) and β = 1 (resp. 0.7). Laser parameters are the same as in Fig. 2 and
Fig. 6, respectively [see also section II A].

fects. The electronic density distribution around the molec- version (8)] one gets
ular centers is reshaped by the instantaneous laser electric ⟨ ⟩ ⟨ ⟩ ⟨ ⟩
field68 . In the context of HHG, given that short trajectories ψb dˆ ψc = ψbS dˆ ψc + ψbO dˆ ψc . (9)
return roughly between successive zeros of that electric field, | {z } | {z }
Scatt.S Scatt.O

20 March 2024 08:11:30

it means that plateau harmonics are emitted around peaks of
the field when such polarization effects are most prominent. In In this picture, the problem is mapped to the interference be-
the context of the factorization in Eq. (2), this suggests that the tween the two “localized” scattering terms Scatt.S/O , based
scattering component should also account for the field dress- on their relative amplitude and phase. Assuming that the two
ing: contributions are approximately out of phase by π (a very
( ) good approximation in the field-free case), their relative am-
Scatt. ν ; θ , ⃗Eν , plitude will determine the depth of the minimum. Intuitively,
the amplitude part is related to the amount of electron den-
sity localized around each thus-defined center. In this section,
where ⃗Eν is the instantaneous electric field at the time of rec-
we revisit our TDDFT results based on that idea and the tran-
ollision for the quantum orbit leading to the HHG energy ν .
sient dressing imposed by the instantaneous driving MIR laser
More practically, the scattering matrix element (7) becomes
field.
⟨ ( ) ( )⟩ To better understand the effects of the transient MIR dress-
ψb ⃗Eν dˆ ψc ν ; θ , ⃗Eν , (8) ing on the bound density, we independently compute static-
field dressed orbitals in OCS. Here as well computations are
where the bound component, and eventually the continuum performed with OCTOPUS39,40 with the same parameters as
too, are dressed by the instantaneous field47 . In the following described in section II A except for the box, which for this
section, we focus on the bound part and revisit our molecular- time-independent calculation is reduced to 20 a.u. in all direc-
frame spectra in the context of transient TCI, driven by sub- tions. The results for θ = 0◦ are shown in Fig. 8. The fig-
cycle polarization effects. ure compares the total density (top row) and the density from
the degenerate highest-occupied molecular orbitals (HOMO,
bottom). From left to right, it shows the density reshaping
imposed by the electric field when the induced force points
IV. TRANSIENT TWO-CENTER INTERFERENCE
from O-to-S (left, with an arrow indicating the force), van-
ishes (middle), and S-to-O (right). Overall and as expected we
Formally, the two-center interference picture of OCS cor- see that the field-free imbalance, biased towards the S-side, is
responds to a decomposition of the bound part of the wave magnified when the force is directed O-to-S (compare the cen-
packet between two components associated with the S and O tral and left columns, respectively). Alternatively, when the
ends of the molecule: ψb = ψbS + ψbO , e.g., rooted in a linear force direction is reversed, its action tends to re-balance the
decomposition of atomic orbital of the bound state. Inject- density components around the two centers (central and right
ing this ansatz in the scattering matrix element [or its dressed columns). For aligned signals, the energies of the dressed or-
Structural Dynamics 8

ends up “destroying” the minimum (|θ | . 15◦ ).

Overall, we see that multidimensional HHS around TCIs
offer a window to observe sub-cycle dynamics in molecules,
between the two centers. The energy of the TCI minimum
serves as the ultrafast clock, through the mapping with the
time of recollision11,12 . The sharpness of the spectral ampli-
tude minimum measures the relative distribution of electron
density between the two centers. The (sign of the) associ-
ated GD feature informs on the orientation of that distribution.
For instance, a symmetry inversion of the bound component
ψb (x) → ψb (−x) in the scattering matrix element (7) [or its
dressed version (8)] leads to a sign change in the GD while
the amplitude is left unchanged.

V. CONCLUSION AND PERSPECTIVES

FIG. 8. Isosurface of the electron density in the total and joint de-
generate highest-occupied molecular orbitals (HOMO) densities of
OCS subjected to a static electric field with polarization parallel to In summary, we have shown that using an APT ionization-
the molecular axis. From left to right, the field strength is that of the seed in TDDFT calculations can produce experimentally-
maximum amplitude of an AC field with 20 TW/cm2 pointing from S relevant HHG spectra. Properly synchronized with the driv-
towards O, no field, and 20 TW/cm2 pointing from O towards S (see
ing MIR field, the APT selects contributions from short quan-
side arrows for the field-induced force direction). All isosurfaces are
tum orbits, which in experimental measurements are filtered
set to 10−8 electrons/a.u.3 . ψb illustrates the conceptual decom-
S/O
through macroscopic effect. Together with the ionization
position of the wave function bound component between the S and
seed, a time window selecting the dipole/acceleration signal
O sides of the molecule – see Eq. (9).
between two consecutive zeros of the electric field can be used
to isolate the contribution from a single set of (short) recollid-
ing orbits to the HHG spectra. This single half-cycle signal

20 March 2024 08:11:30

bitals (not shown) is also important. Indeed, an orientation- then provides a molecular-frame spectroscopic tool that dis-
dependent Stark shift means that orbit contributions scattering criminates between recollision from one end or the other of
from the S and O sides do not accumulate the same amount of the oriented molecule.
phase. This extra bit of phase can also contribute to shifting We have applied this molecular-frame analysis of TCI in
the observed TCI minimum49 . HHG spectra of CO2 and OCS, subjected to a MIR driv-
We now combine the dressed-density picture of Fig. 8 with ing laser field. For the asymmetric case of OCS, we find
molecular-frame HHG spectra of Fig. 7 (b-c) and find con- systematic differences between recolliding from the O and S
sistent agreement with the localized-density qualitative TCI sides of the molecule, which are not compatible with field-free
picture discussed above: First, when the short trajectories rec- TCI geometric effects. Instead, by conceptually decomposing
ollide from the O side – panel (b) – the laser-induced force the bound wave-function between two components associated
points from O to S at the time of recollision, and magnifies the with the S and O ends of the molecule, we understand the
field-free S-to-O imbalance. Accordingly, irrespective of the differences between the two molecular-frame orientations in
orientation angle, no TCI is observed. Second, in the reversed terms of transient polarization effects which reallocate elec-
configuration where recollision happens from the S side – tronic densities between the two “localized” centers. The orig-
panel (c) – the laser force counteracts the field-free imbalance inal imbalance, in the field-free electronic structure, between
and the TCI is apparent for some angles, roughly between 15◦ the S and O ends is either compensated or worsened by the
and 45◦ (see also the thin black guiding curve). Third, the ex- laser force. Depending on the instantaneous electric field at
tinction of the TCI minimum for θ larger than about 45◦ could the time of recollision around the TCI, this leads to either a
be explained by a reduction of polarization effects, due to: (i) sharpening or further extinction of the minimum. Conversely,
orientation. From Ref.22 we know that it is the component of the molecular-frame orientation angle can be used as a tuning
the electric field parallel to the molecular axis that is predom- parameter to control or scan this reshaping. Our analysis also
inantly responsible for “moving” electron densities between stresses the importance of looking at trends with varying such
the two molecular centers. (ii) the TCI location in energy. control parameters. Indeed, individual spectra can be hard to
For larger angles, the TCI moves toward and beyond the cut- read. On the other hand, here, angle-resolved and compari-
off energy, and is thus being probed by recolliding electrons son of members of the OCR (R=O or R=S) family are keys to
that return closer to the zero of the electric field. Both effects understanding transient TCI in our simulations.
participate in reducing the dressing-induced rebalancing be- The mapping between the relative electronic configuration
tween the two centers at larger angles. Finally, and per similar around different groups of the molecule and the spectral prop-
arguments, we wonder if the dressing around parallel orienta- erties of the TCI suggests it provides a good landmark to study
tion, where the expected TCI happens around laser-peak-field ultrafast, sub-cycle, electron dynamics in these systems. Such
amplitude, overcompensates the field-free imbalance and also analyses, however, require a full characterization of the HHG
Structural Dynamics 9

signal, with both intensity and phase/group delay informa- 13 O. Smirnova, Y. Mairesse, S. Patchkovskii, N. Dudovich, D. Villeneuve,
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20 X. Chu, “Time-dependent density-functional-theory calculation of strong-
This work was supported by the US Department of En- field ionization rates of h2 ,” Phys. Rev. A 82, 023407 (2010).
ergy, Office of Science, Office of Basic Energy Sciences, un- 21 A. Sissay, P. Abanador, F. Mauger, M. Gaarde, K. J. Schafer, and K. Lopata,

der Award No. DE-SC0012462. High-performance computa- “Angle-dependent strong-field molecular ionization rates with tuned range-
tional resources were provided by the Louisiana Optical Net- separated time-dependent density functional theory,” J. Chem. Phys. 145,
094105 (2016).
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