Calculation of vertical ionization potentials of hydrogen peroxide by perturbation corrections to Koopmans' theorem

Minato, Taketoshi; Chong, Delano P.

doi:10.1139/v83-096

Cited by 10 publications

(2 citation statements)

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“…H 2 O 2 is readily solvated in water, showing almost no surface preference, and the hydration enthalpy is even larger than for water. , The different hydration of H 2 O 2 and H 2 O is strongly connected with the flexible H 2 O 2 molecular structure, arising from the only weakly hindered rotation of the OH groups about the O−O bond. , The hydrogen peroxide molecule thus possesses another degree of freedom that can be adjusted in the solvation process. In fact, unlike H 2 O, H 2 O 2 is easily distorted by molecular interactions. , Furthermore, H 2 O 2 (aq) is a stronger hydrogen bond donor but a weaker acceptor than H 2 O(aq) …”

Section: Introductionmentioning

confidence: 99%

Flexible H₂O₂ in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations

et al. 2011

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The effect of hydration on the electronic structure of H(2)O(2) is investigated by liquid-jet photoelectron spectroscopy measurements and ab initio calculations. Experimental valence electron binding energies of the H(2)O(2) orbitals in water are, on average, 1.9 eV red-shifted with respect to the gas-phase molecule. A smaller width of the first peak was observed in the photoelectron spectrum from the solution. Our experiment is complemented by simulated photoelectron spectra, calculated at the ab initio level of theory (with EOM-IP-CCSD and DFT methods), and using path-integral sampling of the ground-state density. The observed shift in ionization energy upon solvation is attributed to a combination of nonspecific electrostatic effects (long-range polarization) and of the specific interactions between H(2)O(2) and H(2)O molecules in the first solvation shell. Changes in peak widths are found to result from merging of the two lowest ionized states of H(2)O(2) in water due to conformational changes upon solvation. Hydration effects on H(2)O(2) are stronger than on the H(2)O molecule. In addition to valence spectra, we report oxygen 1s core-level photoelectron spectra from H(2)O(2)(aq), and observed energies and spectral intensities are discussed qualitatively.

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Section: Introductionmentioning

confidence: 99%

Flexible H₂O₂ in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations

et al. 2011

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“…Inspired by already known similarities between POLs and the peroxide molecule (H 2 O 2 ), , we use H 2 O 2 to investigate the variation of HOMO–1 and HOMO with respect to the H–O–O–H dihedral angle. The strong influence of the dihedral angle on many electronic properties of H 2 O 2 has been known for many decades (see for instance ref ); however, to our knowledge, it has never been exploited in the context of POL.…”

Section: Discussionmentioning

confidence: 99%

Correlations between Structural and Optical Properties of Peroxy Bridges from First Principles

et al. 2017

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This work aims at addressing the issue of the optical signature of peroxy bridges by using first-principles methods that combine density functional theory, GW (where G and W stand for one-particle Green function and screened Coulomb potential, respectively), and the solution of a Bethe–Salpeter equation on a bulk amorphous SiO2 model. We demonstrate that the presence of bridges induces broad and weak absorption bands between 3.2 and 7.5 eV. By analyzing the Si–O–O–Si dihedral angle distributions and the corresponding electronic structure, we show that the low overlap between O 2p states involved in the optical transitions together with the dihedral angle site-to-site disorder are at the origin of this weak and broad absorption. Moreover, the energy difference between the two first optical transitions depends linearly on the energy difference between the two first occupied defect-induced electronic states, i.e., depends on the dihedral angle of the bridge. This behavior may explain the longstanding controversy regarding the optical signature of peroxy bridges in amorphous SiO2. Because the correlation is independent of the specific hosting hard material, the results apply whenever the dihedral angle of the bridge has some degree of freedom.

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Half-projected Hartree-Fock calculations for the spectroscopic parameters, frequencies, and intensities of the torsional mode of the lowest lying singlet excited states of hydrogen peroxide

Mukherjee

Senent

Smeyers

1999

Int. J. Quant. Chem.

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Calculation of vertical ionization potentials of hydrogen peroxide by perturbation corrections to Koopmans' theorem

Cited by 10 publications

References 3 publications

Flexible H₂O₂ in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations

Flexible H₂O₂ in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations

Correlations between Structural and Optical Properties of Peroxy Bridges from First Principles

Half-projected Hartree-Fock calculations for the spectroscopic parameters, frequencies, and intensities of the torsional mode of the lowest lying singlet excited states of hydrogen peroxide

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Calculation of vertical ionization potentials of hydrogen peroxide by perturbation corrections to Koopmans' theorem

Cited by 10 publications

References 3 publications

Flexible H2O2 in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations

Flexible H2O2 in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations

Correlations between Structural and Optical Properties of Peroxy Bridges from First Principles

Half-projected Hartree-Fock calculations for the spectroscopic parameters, frequencies, and intensities of the torsional mode of the lowest lying singlet excited states of hydrogen peroxide

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Product

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About

Flexible H₂O₂ in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations

Flexible H₂O₂ in Water: Electronic Structure from Photoelectron Spectroscopy and Ab Initio Calculations