A theoretical library of N1s core binding energies of polynitrogen molecules and ions in the gas phase

Du, Xinzhe; Wang, Sheng-Yu; Wei, Minrui; Zhang, Junrong; Ge, Guoyan; Hua, Weijie

doi:10.1039/d2cp00069e

Cited by 21 publications

(12 citation statements)

References 70 publications

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“…Indeed, our calculated value is 0.22 eV lower than the experimental one (see Table 4). The DFT result of Chong and Hu 18 is only 0.11 eV lower, while that calculated by Du et al 19 differs by 0.45 eV. The condensed phase measurement result is lower by about 4 eV than our gas-phase value.…”

Section: Resultscontrasting

confidence: 84%

“…For comparison, the theoretical CEBEs have been calculated at the ΔM06-2X//mixed basis set level. These values and the results of other authors 17–19 are also shown in Table 4.…”

Section: Resultssupporting

confidence: 60%

“…17 The molecular core binding energies have been calculated for isoxazole using density functional theory (DFT). 18,19 In the present work, we focus on interpreting the near-edge X-ray absorption fine structure spectra of the gas-phase isoxazole molecule measured at the C, N, and O K-edges. To aid in disentangling the spectral features, we have used the timedependent density functional theory with the short-range corrected SRC2-BLYP exchange-correlation functional.…”

Section: Introductionmentioning

confidence: 99%

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Core–shell excitation of isoxazole at the C, N, and O K-edges – an experimental NEXAFS and theoretical TD-DFT study

Wąsowicz

Ljubić

Kivimäki

et al. 2022

Phys. Chem. Chem. Phys.

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Section: Resultscontrasting

confidence: 84%

“…For comparison, the theoretical CEBEs have been calculated at the ΔM06-2X//mixed basis set level. These values and the results of other authors 17–19 are also shown in Table 4.…”

Section: Resultssupporting

confidence: 60%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Core–shell excitation of isoxazole at the C, N, and O K-edges – an experimental NEXAFS and theoretical TD-DFT study

Wąsowicz

Ljubić

Kivimäki

et al. 2022

Phys. Chem. Chem. Phys.

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“…DFT is the most efficient electronic structure method to model the core hole states and the core level binding energies. In the gas phase, the ΔKS approach has been validated to produce accurate absolute core IPs with a sub-electronvolt accuracy. − The detailed number of mean absolute deviation (MAD) depends on the test sets, DFT functionals, and the edges. For instance, typically 0.5–1.0 eV was summarized by Bagus et al for IPs at different K-edges of light elements (C/N/O/F); 0.81 and 0.21 eV were reported by Pueyo Bellafont et al based on PBE and TPSS calculations for a test set of 68 molecules of light atoms (B/C/N/O/F 1s edges) or 0.3 eV by our group based on a test set of 20 molecules with the BP86 functional (N 1s edge only).…”

Section: Discussionmentioning

confidence: 99%

A QM/MM Study on the X-ray Spectra of Organic Proton Transfer Crystals of Isonicotinamides

Zhang

Wang

et al. 2022

J. Phys. Chem. C

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Proton transfer (PT) in organic crystals creates localized charges and strong hydrogen bonding (HB), making the self-consistent field (SCF) calculation of core-ionized and core-excited states challenging. Today most corresponding X-ray spectral measurements are interpreted based on empirical fitting and/or chemical intuitions. Here we present a systematic quantum mechanical/molecular mechanical (QM/MM) study of N 1s X-ray photoelectron (XPS) and absorption (XAS) spectra of three isonicotinamide (IN)-based organic crystals with full (1), half (2), and no (3) protonations. A complete picture of the structure–spectroscopy relation in different crystal environments was provided, and assignments to three unprotonated (pyridinic, p; amide, a 1 and a 2) sites and one protonated (pyridinic, h) N site were clearly made. We found that including distant residues as natural population analysis (NPA) point charges can effectively enhance the SCF convergence of the core states. The size of the QM part was tuned, and with some 140–170 atoms we achieved spectral convergence that can represent the infinite crystal. At the crystal structures, simulated relative binding energies deviate ≤0.3 eV to experiments. Simulated XAS spectra agree well with experiments, and with molecular orbital analysis we interpreted the π* structures as hybrid local excitation and charge transfer states (πLE–CT *) or pure LE states (πLE *). Analyses on both spectra helped understand the PT and HB nature in such organic crystals, and a debate in XPS interpretation of 3 was resolved and its XAS assignment corrected. Further, to model the dynamical effect of the proton in 2, XPS/XAS spectra were evaluated at snapshots with varying N–H distances. A continuous picture illustrates the sensitive influence of proton position to both spectra. Reduction of the N–H distance by only 0.2 Å from the crystal structure (1.1 Å) excellently reproduced both spectra. This perturbation phenomenologically models effects of vibration from the equilibrium crystal structure and environmental temperature and pressure factors.

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“…DFT usually can predict 1s binding energies with a sub-eV accuracy. The detailed value of the averaged deviation depends on test systems, functionals, and edges, for example, 0.3 eV 50 for some 20 molecules at the N 1s edge, or 0.5−1.0 eV 51 for several K-edges of light elements. In this work, we achieved excellent agreement with experiments in absolute BEs, with deviations of only 0.17, 0.15, and 0.09 eV for phenanthrene, coronene, and naphthalene.…”

Section: Structure Of the Core-ionized State Andmentioning

confidence: 99%

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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A theoretical library of N1s core binding energies of polynitrogen molecules and ions in the gas phase

Abstract: Polynitrogen molecules and ions are important building blocks of high energy density compounds(HEDCs). High energy bonds formed at the N sites can be effectively probed by the X-ray photoelectron spectroscopy...

Cited by 21 publications

References 70 publications

Core–shell excitation of isoxazole at the C, N, and O K-edges – an experimental NEXAFS and theoretical TD-DFT study

Core–shell excitation of isoxazole at the C, N, and O K-edges – an experimental NEXAFS and theoretical TD-DFT study

A QM/MM Study on the X-ray Spectra of Organic Proton Transfer Crystals of Isonicotinamides

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

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