Breaking inversion symmetry by protonation: experimental and theoretical NEXAFS study of the diazynium ion, N<sub>2</sub>H<sup>+</sup>

Couto, Rafael C.; Hua, Weijie; Lindblad, Rebecka; Kjellsson, Ludvig; Sorensen, S. L.; Kubin, Markus; Bülow, Christine; Timm, Martin; Zamudio-Bayer, Vicente; Issendorff, Bernd von; Söderström, Johan; Lau, J. Tobias; Rubensson, J.‐E.; Ågren, Hans; Carravetta, Vincenzo

doi:10.1039/d1cp02002a

Cited by 12 publications

(11 citation statements)

References 57 publications

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“…In multiatom molecules, this can be caused by dynamic vibronic coupling (26)(27)(28), and for diatomics, an external disturbance may also break the symmetry. This is the case for adsorbed molecules (29), and recently, it has been demonstrated that protonation of N 2 molecules opens the XAS channel corresponding to parity-forbidden transitions in the symmetric molecule (30). Weak interactions between oxygen molecules and the surrounding are vital for numerous important processes, e.g., in reversible binding to metal complexes, which is essential in enzymatic and catalytic processes (31).…”

Section: Discussionmentioning

confidence: 99%

Parity violation in resonant inelastic soft x-ray scattering at entangled core holes

Söderström,

Ghosh,

Kjellsson

et al. 2024

Sci. Adv.

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Resonant inelastic x-ray scattering (RIXS) is a major method for investigation of electronic structure and dynamics, with applications ranging from basic atomic physics to materials science. In RIXS applied to inversion-symmetric systems, it has generally been accepted that strict parity selectivity applies in the sub–kilo–electron volt region. In contrast, we show that the parity selection rule is violated in the RIXS spectra of the free homonuclear diatomic O 2 molecule. By analyzing the spectral dependence on scattering angle, we demonstrate that the violation is due to the phase difference in coherent scattering at the two atomic sites, in analogy with Young’s double-slit experiment. The result also implies that the interpretation of x-ray absorption spectra for inversion symmetric molecules in this energy range must be revised.

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Section: Discussionmentioning

confidence: 99%

Parity violation in resonant inelastic soft x-ray scattering at entangled core holes

Söderström,

Ghosh,

Kjellsson

et al. 2024

Sci. Adv.

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“…By contrast, in case when a −CN group is substituted to benzene (i.e., benzonitrile), out-of-plane modes can be active in the N 1s XAS spectrum . In analogy to this, bending modes in a linear cation NH 2 + were found to be active and special (double-well potential energy surface in the final state), where one of the modes was treated independently with numerical solution of the one-dimensional Schrödinger equation …”

Section: Discussionmentioning

confidence: 99%

“…First, low-frequency (less than 800 cm −1 ) in-plane ring deformations. These include ν (7,9,12,16,17), ν (13), and ν (5,7,9,16)…”

Section: Phenanthrene Figurementioning

confidence: 99%

“…Early vibrational fine-structure studies in XPS spectra dated to the 1960s, when asymmetry in spectral peaks was found in the gas-phase spectra of small molecules. With the continuous improvement of spectral resolution in synchrotron radiation facilities in recent decades, high-resolution X-ray spectra, especially XPS and X-ray absorption spectroscopy (XAS), enabled the identification of vibronic fine structures of molecules and ions, which attracted the broad interests of experimentalists and theoreticians. − For example, in a recent study with the Elettra beamline, eight peaks were clearly resolved within a narrow region of 1.5 eV (290.5–292 eV) in the C 1s XPS spectrum of pyridine.…”

Section: Introductionmentioning

confidence: 99%

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Vibrationally-Resolved X-ray Photoelectron Spectra of Six Polycyclic Aromatic Hydrocarbons from First-Principles Simulations

et al. 2022

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Vibrationally resolved C 1s X-ray photoelectron spectra (XPS) of a series of six polycyclic aromatic hydrocarbons (PAHs; phenanthrene, coronene, naphthalene, anthracene, tetracene, and pentacene) were computed by combining the full core hole density functional theory and the Franck−Condon simulations with the inclusion of the Duschinsky rotation effect. Simulated spectra of phenanthrene, coronene, and naphthalene agree well with experiments both in core binding energies (BEs) and profiles, which validate the accuracy of our predictions for the rest molecules with no high-resolution experiments. We found that three types of carbons i (inner C), p (peripheral C bonded to three C atoms), and h (peripheral C bonded to an H atom) show decreasing BEs. In linear PAHs (the latter four), h-type carbons further split into h1 or h2 (on inner or edge benzene ring) subtypes with chemical shifts of ca. 0.2−0.4 eV. All major Franck− Condon-active modes are characterized to be in-plane vibrations: low-frequency (<800 cm −1 ) C−C ring deformation modes play an essential role in determining the peak asymmetries; and for each h-type carbon a high-frequency (ca. 3600 cm −1 ) C*−H stretching mode is responsible for the high-energy tail. We found that core ionization leads to reduction of all C*−C and C*−H bond lengths and ring deformation with a definite direction. Based on theoretical spectra of four linear PAHs, we found asymptotic relations and anticipated possible spectral features for even larger linear PAHs. Our calculations provide accurate reference spectra for XPS characterizations of PAHs, which are useful in understanding the vibronic coupling effects in this family.

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“…The method modulates the effect of electron disappearance by adding a nuclear charge, which provides a similar electronic potential for the core-hole state. The ECH method has been successfully applied to a variety of separated systems as well as infinite/periodic systems. ,− Numerous studies have demonstrated that the ECH method is reliable and practical for macromolecular systems. The NEXAFS spectra were performed by using the PSSXS program ,, interfaced to the Gaussian 16 package .…”

Section: Computation Methodsmentioning

confidence: 99%

Theoretic Study of Sulfur-Doped Graphdiynes by X-ray Spectroscopy

Qi,

Ge,

Wang

et al. 2023

Inorg. Chem.

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Sulfur-doped graphdiyne at different sites has a tremendous impact on its electronic structure and properties. Due to the large number of S-doping sites, there is no comprehensive and systematic experimental and theoretical study regarding the identification of S-doped graphdiyne configurations. In this paper, X-ray photoelectron (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra as well as geometries of 10 sulfurdoped graphdiyne molecules have been simulated at the density functional theory (DFT) level. Different types of carbon spectra were theoretically modeled to analyze the contribution of the spectra. Calculated results show that the NEXAFS spectra exhibit a clear dependence on the local structure. The theoretically simulated XPS spectra are in good agreement with the experimental spectra. The XPS spectra combined with the NEXAFS spectra can provide effective information for identifying the 10 S-doped conformations. Our research results provide further theoretical prediction and guidance for the experimental synthesis of S-doped graphdiyne, which solves the difficult problem of identification of S-doped carbon-based materials.

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Breaking inversion symmetry by protonation: experimental and theoretical NEXAFS study of the diazynium ion, N₂H⁺

Abstract: As an example of symmetry breaking in NEXAFS spectra of protonated species we present a high resolution NEXAFS spectrum of protonated dinitrogen, the diazynium ion N2H+. By ab-initio calculations we...

Cited by 12 publications

References 57 publications

Parity violation in resonant inelastic soft x-ray scattering at entangled core holes

Parity violation in resonant inelastic soft x-ray scattering at entangled core holes

Vibrationally-Resolved X-ray Photoelectron Spectra of Six Polycyclic Aromatic Hydrocarbons from First-Principles Simulations

Theoretic Study of Sulfur-Doped Graphdiynes by X-ray Spectroscopy

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Breaking inversion symmetry by protonation: experimental and theoretical NEXAFS study of the diazynium ion, N2H+

Abstract: As an example of symmetry breaking in NEXAFS spectra of protonated species we present a high resolution NEXAFS spectrum of protonated dinitrogen, the diazynium ion N2H+. By ab-initio calculations we...

Cited by 12 publications

References 57 publications

Parity violation in resonant inelastic soft x-ray scattering at entangled core holes

Parity violation in resonant inelastic soft x-ray scattering at entangled core holes

Vibrationally-Resolved X-ray Photoelectron Spectra of Six Polycyclic Aromatic Hydrocarbons from First-Principles Simulations

Theoretic Study of Sulfur-Doped Graphdiynes by X-ray Spectroscopy

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Breaking inversion symmetry by protonation: experimental and theoretical NEXAFS study of the diazynium ion, N₂H⁺