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Strong-Field Dissociation of O2+:

Exploring Bond Stabilization and
Mapping Light-Induced Potentials*
Paul M. Abanador
* Department of Physics, Kansas State University

Research Talk
Ateneo de Manila University
May 15, 2023

Paul Abanador – Research Talk (ADMU)

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Ultrafast Dynamics in Molecules

 Time-resolved Imaging of Molecular Systems using
Intense, Ultrafast Laser Pulses
 High Harmonic Spectroscopy
 Photofragment Spectroscopy

 Dissociation Dynamics in O2+

 Molecular Bond Stabilization
 Mapping of Light-Induced Potentials (LIPs)

Abanador et al., Phys. Rev. A 101, 043410 (2020)

Abanador and Thumm, Phys. Rev. A 102, 053114 (2020)

Paul Abanador – Research Talk (ADMU)

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Ultrafast Phenomena in Molecules:

Charge Migration
 Charge migration refers to the
ultrafast motion of the “hole”
triggered by strong-field (SF)
ionization or excitation.
 Subfemtosecond time scale
(1 fs = 10-18 s)
TDDFT calculations:
 Primarily driven by electron Removal of a core-level
correlation and relaxation electron in nitrosobenzene
J. Phys. Chem. Lett. 8, 3991 (2017)

Paul Abanador – Research Talk (ADMU)

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Probing Ultrafast Dynamics in Molecules:

Self-probing scheme
 High harmonic spectroscopy
 The returning electron wave packet serves as
self-probe of the cation from which it is ionized.

Charge migration in
iodoacetylene.
Kraus, et al. (2015)

Paul Abanador – Research Talk (ADMU)

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Probing Ultrafast Dynamics in Molecules:

Pump-probe scheme
 Dynamics initiated by an XUV pump
pulse and later probed by an IR pulse.
 Photofragment spectroscopy:
oscillation in the doubly charged ion
yields with a half-period of fs.

Taking snapshots of
the hole dynamics.
Calegari, et al. (2014)
Paul Abanador – Research Talk (ADMU)
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Theoretical Perspective
 In general, coupling to nuclear
 QM calculations of the “full
motion needs to be included.
dynamics” might be possible
 And there is usually an external field in cases of small molecules.
(or intense laser pulse) present
during the relevant dynamics. 𝜕
𝑖 Ψ ( 𝒓 ,𝑡 )= 𝐻 ( 𝒓 , 𝑡 ) Ψ ( 𝒓 , 𝑡 )
𝜕𝑡
 Why study diatomic molecules?
 Open questions about fundamental
aspects of SF molecular dissociation
(first predicted by Floquet theory) ⃗
𝑅 +
𝜃
 Bond stabilization vs. rotational + ⃗
𝐸 (𝑡 )
dynamics, mapping of LIPs

Paul Abanador – Research Talk (ADMU)

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LIPs in Diatomic molecules
Dissociation mechanisms in H2+ molecular ion
 Field-dressed states from
Floquet theory
 Based on the solution of the
TDSE for a potential with
temporal periodicity
 Molecular effects such as
bond softening and bond
hardening (or vibrational
trapping)
Ibrahim et al., J. Phys. B 51, 042002 (2018).

 Application of Floquet theory (Bandrauk and Sink, 1981 and Chu, 1981).
 Experimental study of bond softening (Bucksbaum et al., 1990).

Paul Abanador – Research Talk (ADMU)

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LIPs in Diatomic molecules
Light-induced potentials in D2+
 Laser-molecule interaction
⃗ produces a light-induced
Energy (eV)

𝐸 (𝑡 )
conical intersection (LICI).
2
𝐼 eff =𝐼 0 cos ( 𝜃)
⃗
𝐸 (𝑡 )
𝐸 eff =𝐸0 cos ( 𝜃)
R (Å) (rad )
θ
Halasz et al., J. Phys. Chem. Lett. 6, 348 (2015).
Angular distributions of fragments from H2+
 Modulation in the
angular distributions of
fragments > quantum
interferences via LICIs.
Natan, Bucksbaum, et al., Phys. Rev. Lett. 116, 143004 (2016).
Paul Abanador – Research Talk (ADMU)
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Numerical methods fs
Delay is fixed.
 Coupled-state propagation (TDSE)*
 Ψ1   TR  V1 D12  Ψ1  V2 )
d    
dissociation
O2+
i  Ψ 2    D 21 TR  V2  Ψ 2 
dt      

       

Energy
dipole coupling: Dij = dij(R)E(t) V1 )

with the total density written as fs O2

ρ (R,t)  i ρ i (R,t)  i | i ( R , t ) |2
FC: rapid ionization
*derived from a BO approximation of ()
the rovibronic dynamics (including R
electronic degree of freedom)

Paul Abanador – Research Talk (ADMU)

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Numerical methods Dissociative ionization of O2+
 For O2+, two relevant channels
were previously identified: dissociation
3ω
and ω O + O+

 Highest dipole coupling strength

(calculated using GAMESS).
pump
 Can explain some features in
measured pump-probe delay-
dependent O+ ion yields, e.g.,
oscillation period of about 34 fs *

*Magrakvelidze et al., Phys. Rev. A 86, 023402 (2012)

Cörlin et al., Phys. Rev. A 91, 043415 (2015)
Xue et al., Phys. Rev. A 97, 0434 (2018)
Malakar et al., Phys. Rev. A 98, 013418 (2018)
Abanador et al., Phys. Rev. A 101, 043410 (2020)

Paul Abanador – Research Talk (ADMU)

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Main results: Bond stabilization
Pulse duration dependence of total dissociation probability (integrated over )

1D – without rotations
2D – including rotations 800 nm

 Nonmonotonic dependence of Ptot with respect to pulse duration

 Suppression of the dissociation yield persists in rotating molecules

Abanador et al., Phys. Rev. A 101, 043410 (2020)

Paul Abanador – Research Talk (ADMU)
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Main results: Bond stabilization
1D – without rotations
2D – including rotations
 We apply a continuous-wave field to
explain the underlying mechanism:
 Transient trapping of nuclear
probability during the dissociation
process.
 This analysis reveals QB frequencies
related to the time scale for BH
mechanism and explains the onset of
bond stabilization for long pulses.
Fourier analysis of dynamics in a
continuous wave field with ramp-up.

Abanador et al., Phys. Rev. A 101, 043410 (2020)

Paul Abanador – Research Talk (ADMU)
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Main results: Mapping of LIPs
 We first consider the case with Calculated KER spectra (lowest intensity)
the lowest peak intensity.
 1D and 2D results are very
similar
 fringe structures that shift
downward in energy for angles,
to .
 For comparison, the Floquet 40-fs pulse, 800 nm, W/cm2
model is also shown (black
dashed curves).* (a) - Total angle-integrated KER spectra
(b),(c) - Angle-resolved KER spectra

*See additional slides

Abanador and Thumm, Phys. Rev. A 102, 053114 (2020)
Paul Abanador – Research Talk (ADMU)
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Main results: Mapping of LIPs
 The Floquet prediction agrees
Calculated KER spectra (lowest intensity)
very well with the KER fringe
structures in the TDSE results.
 We looked at several laser pulse
intensities and we generally find
very good agreement.*

40-fs pulse, 800 nm, W/cm2

(a) - Total angle-integrated KER spectra

(b),(c) - Angle-resolved KER spectra
*See additional slides

Abanador and Thumm, Phys. Rev. A 102, 053114 (2020)

Paul Abanador – Research Talk (ADMU)
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Main results: Mapping of LIPs
Angular distribution of photofragments

(d) W/cm2
(e) W/cm2
(f) W/cm2

 We find modulations in both the 1D and 2D results, which reflects

the (angle-dependent) fringe structures in the KER spectra.
 The frequency of the modulations varies drastically over the
range of intensities that we considered.
 In the 2D results, we see shifts in the modulations toward pi/2
(due to the LICI feature in the LIP).
Abanador and Thumm, Phys. Rev. A 102, 053114 (2020)
Paul Abanador – Research Talk (ADMU)
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Summary and Outlook

 We provide proof-of-concept studies for future experiments.
 Molecular bond stabilization persisting in rotating molecules
 Mapping of the LIPs in the observable angle-resolved KER spectra
 LICI feature becomes significant in higher laser pulse intensities
 There is no “one-size-fits-all” answer!
 How and to what extent (observables)? When (laser pulses,
molecules)? Where (KER range)?
 Challenges in theory (quantitative comparison with expt.)
 Multiple ionization, 3-photon processes, recollision excitations, etc.

Paul Abanador – Research Talk (ADMU)

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Acknowledgments
 LSU: Kenneth Schafer, Mette Gaarde, Kenneth Lopata,
Francois Mauger
 KSU: Uwe Thumm, Christine Aikens, Thomas Pauly (REU)
 Experimental collaborators: UVa, OSU, KSU

Paul Abanador – Research Talk (ADMU)

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Additional slides (Floquet analysis)

 Floquet description of dissociation (1D in R)
 Explain mechanism behind the features that
we find in the TDSE results for laser peak
intensities of 1013–1014 W/cm2.
 Outline of the Floquet analysis
 Obtain the light-induced potentials at ,
and.*
 For each alignment angle and , calculate the
vibrational energies in
the upper Floquet curve.
 The comparison with KER values is given by
.

*neglect effects due to the temporal variation of the LIPs.

800 nm, W/cm2
Paul Abanador – Research Talk (ADMU)
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Additional slides (TDSE results)

Intensity dependence of the LIPs
 For higher laser intensities (up to
1014 W/cm2), we see qualitative
agreement between our TDSE
results and the Floquet model.
 Strong evidence for the and
dependence of the LIPs

 By comparing to the 1D and 2D

results, we can observe some
effects due to rotational
excitations.

Paul Abanador – Research Talk (ADMU)