Reconstruction of the time-dependent electronic wave packet arising from molecular autoionization

Bello, Roger Y.; Canton, Sophie E.; Jelovina, Denis; Bozek, John D.; Rude, B.; Smirnova, Olga; Ivanov, Misha; Palacios, Alicia; Martín, Fernando

doi:10.1126/sciadv.aat3962

Cited by 17 publications

(14 citation statements)

References 49 publications

(65 reference statements)

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“…This simplicity is crucial to extract structural information, such as bond distances, directly from the frequency of the observed oscillations 13,26 . It also explains why v -ratios resulting from H 2 photoionization have recently permitted to reconstruct the subfemtosecond time evolution of the electron wave packet that arises from H 2 autoionization, thus forgoing ultrashort light pulses 19 …”

Section: Introductionmentioning

confidence: 99%

Full-dimensional theoretical description of vibrationally resolved valence-shell photoionization of H2O

Engin

González‐Vázquez

Maliyar

et al. 2019

Structural Dynamics

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We have performed a full-dimensional theoretical study of vibrationally resolved photoelectron emission from the valence shell of the water molecule by using an extension of the static-exchange density functional theory that accounts for ionization as well as for vibrational motion in the symmetric stretching, antisymmetric stretching, and bending modes. At variance with previous studies performed in centrosymmetric molecules, where vibrationally resolved spectra are mostly dominated by the symmetric stretching mode, in the present case, all three modes contribute to the calculated spectra, including intermode couplings. We have found that diffraction of the ejected electron by the various atomic centers is barely visible in the ratios between vibrationally resolved photoelectron spectra corresponding to different vibrational states of the remaining H2O+ cation (the so-called v-ratios), in contrast to the prominent oscillations observed in K-shell ionization of centrosymmetric molecules, including those that only contain hydrogen atoms around the central atoms, e.g., CH4. To validate the conclusions of our work, we have carried out synchrotron radiation experiments at the SOLEIL synchrotron and determined photoelectron spectra and v-ratios for H2O in a wide range of photon energies, from threshold up to 150 eV. The agreement with the theoretical predictions is good.

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Section: Introductionmentioning

confidence: 99%

Full-dimensional theoretical description of vibrationally resolved valence-shell photoionization of H2O

Engin

González‐Vázquez

Maliyar

et al. 2019

Structural Dynamics

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“…Þ + e − (the so called v-ratios). 101 Very prominent structures can be seen in the range of photon energies 24-37 eV. These structures are due to autoionization from the lowest Q 1 1 Σ + u and Q 2 1 Π u doubly excited states of H 2 , which lie above the first (1sσ g ) and the second (2pσ u ) ionization thresholds, respectively, as shown in the left panel of Figure 5.…”

Section: Molecular Photoionizationmentioning

confidence: 86%

“…In particular, we consider the case of H 2 photoionization by synchrotron radiation. Figure shows a comparison between measured and calculated vibrationally resolved photoionization cross sections referred to the dominant ionization channel H 2 + hν →

H_{2}^{+} ((), v = 2)

+ e − (the so called v ‐ratios) . Very prominent structures can be seen in the range of photon energies 24–37 eV.…”

Section: Molecular Photoionizationmentioning

confidence: 99%

“…In general, the slower the autoionization, the higher the vibrational state in which

H_{2}^{+}

is left, because the rapidly evolving nuclear wave packet accumulates higher momentum, thus ionizing into higher vibrational states of

H_{2}^{+}

(1s σ g ). Therefore, the nuclear motion acts as an internal clock of autoionization and the line shapes of the peaks observed in vibrationally resolved photoelectron spectra provide snapshots of the autoionization dynamics through a direct time‐energy mapping …”

Section: Molecular Photoionizationmentioning

confidence: 99%

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The quantum chemistry of attosecond molecular science

Palacios

Martı́n

2019

WIREs Comput Mol Sci

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With the advent of attosecond light pulses at the beginning of this century, the possibility to perform real-time observations of electron motion in molecules has spurred impressive theoretical developments aimed at providing support and guidance to numerous, but still incipient, experimental efforts devoted to understand chemistry at its ultimate temporal frontier: the attosecond. The first real-time observation of electron dynamics in a relatively large molecule, phenylalanine, was reported in 2014. This would have been difficult without the help of theory, since observations in this emerging field, recently coined attochemistry, are still indirect.While standard Quantum Chemistry methods can describe excited bound-state dynamics, new approaches incorporating scattering theory formalisms are needed to understand the interaction with attosecond pulses. Indeed, due to their short wavelengths, lying in the XUV and X-ray spectral regions, the interaction of such pulses with any molecule inevitably leads to ionization, which requires describing the molecular ionization continuum. Also, because of their short duration (i.e., large bandwidth), ionization is accompanied by the formation of a molecular electronic wave packet (i.e., a coherent superposition of electronic states), which evolves in time and dictates the fate of the molecule at the longer time scales where chemistry shows up. Although much has already been done up to date, current bottlenecks in the field are to account for electron correlations during the ionization process and for the coupled electron and nuclear dynamics that follows. Past and ongoing theoretical efforts are described here along with experimental work towards the solid establishment of attochemistry. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Quantum Chemistry Theoretical and Physical Chemistry > Spectroscopy K E Y W O R D S attochemistry, attosecond dynamics, molecular dynamics, molecular ionization, ultrafast

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“…The presence of continuum-embedded discrete states can lead to interference effects, a paradigmatic example being the Fano resonance, where the scattering amplitudes of a resonant (discrete) and background (continuum) process interfere to give rise to the classic asymmetric line shape [18]. In photoionization, continuum states that decay via autoionization can provide an indirect channel to target states that can interfere with the direct ionization channel to those very same states [19][20][21][22][23]. This effect can be observed in a PAD [20,24,25], where the amplitudes and phases of the angular momentum components of the photoelectron scattering wave…”

Section: Introductionmentioning

confidence: 99%

Role of dipole-forbidden autoionizing resonances in nonresonant one-color two-photon single ionization of N2

et al. 2020

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Reconstruction of the time-dependent electronic wave packet arising from molecular autoionization

Abstract: The time evolution of an electronic molecular wave packet is determined using nuclear motion as an internal clock of the system.

Cited by 17 publications

References 49 publications

Full-dimensional theoretical description of vibrationally resolved valence-shell photoionization of H2O

Full-dimensional theoretical description of vibrationally resolved valence-shell photoionization of H2O

The quantum chemistry of attosecond molecular science

Role of dipole-forbidden autoionizing resonances in nonresonant one-color two-photon single ionization of N2

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