Multidimensional molecular high-harmonic spectroscopy: A road map for charge migration studies

Tuthill, Daniel R.; Mauger, F.; Scarborough, Timothy D.; Jones, Robert R.; Gaarde, Mette B.; Lopata, Kenneth A.; Schafer, Kenneth J.; DiMauro, Louis F.

doi:10.1016/j.jms.2020.111353

Cited by 20 publications

(16 citation statements)

References 108 publications

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“…seeded results for CS 2 and CSe 2 also agree well with the other results, whereas for CO 2 , the APT-seeded results are substantial outliers. Taken together, these results illustrate the benefits of comparing spectral features across multiple dimensions [52,55] -here, the laser fields and the carbon-dichalcogen family -to identify both generic spectroscopic features that can be compared against each other and signatures that are unique to a system.…”

Section: Resultsmentioning

confidence: 71%

Orbital-resolved calculations of two-center interferences in linear triatomic molecules

et al. 2021

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We perform ab initio calculations of high-harmonic spectroscopy (HHS) of two-center interference phenomena in oriented carbon dichalcogen molecules, using time-dependent density functional theory (TDDFT). We show that, by resolving the harmonic response into contributions from individual Kohn-Sham orbitals, we can extract target-specific characteristics for both the spectral amplitude and phase. We also discuss that this extraction is predicated on a careful analysis and normalization of the harmonic spectrum. Finally, we present field-free scattering calculations that mimic the recollision step in high-order harmonic generation and allow the calculation of recombination dipole matrix elements without explicitly calculating the scattering states of a molecule. We show that the orbital-resolved TDDFT HHS results and results based on our field-free scattering calculations are in very good agreement with each other.

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Section: Resultsmentioning

confidence: 71%

Orbital-resolved calculations of two-center interferences in linear triatomic molecules

et al. 2021

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“…Conceptually, writing the bound wave packet as a linear combination of atomic orbitals, ψ b = ψ b 1 + ψ b 2 , the RDME becomes , ⟨ ψ b false| d̂ false| ψ c ⟩ = ⟨ ψ b 1 false| d̂ false| ψ c ⟩ + ⟨ ψ b 2 false| d̂ false| ψ c ⟩ where ψ c is the continuum electron wavepacket and d ̂ is the dipole operator. The two centers in the HOMO of CO 2 have equal charge density.…”

Section: Description Of Interferencesmentioning

confidence: 99%

Investigation of Interferences in Carbon Dioxide through Multidimensional Molecular-Frame High-Harmonic Spectroscopy

et al. 2022

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We present molecular-frame high-harmonic spectroscopic measurements of the spectral intensity and group delay of carbon dioxide. Using four different driving wavelengths and a range of intensities at each wavelength for high-harmonic generation, we observe a well-characterized minimum in the harmonic emission that exhibits both a wavelength and intensity dependence. Using the intensity dependence at each driving wavelength, we classify the minimum as due to either a structural two-center interference or dynamic multichannel interference, consistent with previous literature. By additionally measuring the group delay at each driving wavelength and intensity, we find that the sign of the group delay excursion across the interference is an acute probe of the interference mechanism. The experimental results are confirmed by ab initio time-dependent density functional theory calculations of both the spectral intensity and the phase of the harmonic emission.

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“…At the time of recombination, the information of the electron wave packet of the cation is encoded in both the amplitude and phase of each generated harmonic. The intrinsic time-to-frequency mapping underlying HHG allows a temporal measurement of the electron dynamics with a resolution of tens to a hundred attoseconds [25][26][27][28][29][30]. Up to now, HHS has been well used for ultrafast molecular detection with both attosecond temporal [25][26][27][28][29][30] and ångström spatial resolutions [31][32][33].…”

Section: Introductionmentioning

confidence: 99%

Attosecond probing and control of charge migration in carbon-chain molecule

Lan

He²,

et al. 2023

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In quantum mechanics, when an electron is quickly ripped off from a molecule, a superposition of new eigenstates of the cation creates an electron wave packet that governs the charge flow inside which has been called charge migration (CM). Experimentally, to extract such dynamics at its natural (attoseconds) timescale is quite difficult. Here, we report the first such experiment in a linear carbon-chain molecule, butadiyne (C4H2), via high harmonic spectroscopy (HHS). By employing advanced theoretical and computational tools, we showed that the wave packet and the CM of a single molecule is reconstructed from the harmonic spectra for each fixed-in-space angle of the molecule. For this one-dimensional molecule, we calculate the center of charge (t) to obtain v_{cm}, to quantify the migration speed and how it depends on the orientation angle. The findings also uncover how the electron dynamics at the first few-tens to hundreds attoseconds depends on molecular structure. The method can be extended to other molecules where HHS technique can be employed.

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Multidimensional molecular high-harmonic spectroscopy: A road map for charge migration studies

Cited by 20 publications

References 108 publications

Orbital-resolved calculations of two-center interferences in linear triatomic molecules

Orbital-resolved calculations of two-center interferences in linear triatomic molecules

Investigation of Interferences in Carbon Dioxide through Multidimensional Molecular-Frame High-Harmonic Spectroscopy

Attosecond probing and control of charge migration in carbon-chain molecule

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