Configuration interaction and relaxation effects on generalized and optical oscillator strengths of the H2O molecule: The X1A1→A1B1 transition

We report an angle-resolved electron energy loss spectroscopy (EELS) study on the valence-shell electronic excitations in CF(4). Experimentally momentum-transfer-dependent generalized oscillator strengths (GOSs) or GOS profiles for low-lying electronic excitations at 12.6, 13.8, and 14.8 eV are derived from EELS spectra measured at an incident electron energy of 3 keV. We also calculate GOS profiles using theoretical wave functions at the equation-of-motion coupled cluster singles and doubles level. There are good agreements between experiment and theory except for a significant discrepancy at small momentum transfer for the 1t(l) → 3s Rydberg excitation at 12.6 eV. The experimental GOS profile for 1t(l) → 3s exhibits a shape that is typical of a dipole allowed transition, while the excitation is formally dipole forbidden. This symmetry breaking behavior is rationally accounted for by qualitatively analyzing the nature of vibronic coupling effects. For the excitation band at 13.8 eV, a shoulder and extrema are observed in the GOS profile and are then found to be mainly due to the 2(1)T(2) transition. Furthermore, the theoretical GOS profile for the 2(1)T(2) transition exhibits a remarkable oscillatory pattern; its origin is discussed by considering multicenter interference effects. For the 14.8 eV excitation band, the predominant nondipole nature of the underlying transitions are revealed and comparisons with the theoretical calculations show that major contributions to this band come from the 4t(2) → 3p excitation.

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Experimental and theoretical study on generalized oscillator strengths of the valence-shell electronic excitations in CF4

Watanabe

Suzuki

Takahashi

2011

The Journal of Chemical Physics

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Generalized oscillator strengths of carbon disulfide calculated by multireference configuration interaction

Oliveira

Jalbert

Rocha

2019

The Journal of Chemical Physics

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Transition energies and generalized oscillator strengths (GOSs) for transitions up to 6.3 eV of carbon disulfide were calculated at the multireference configuration interaction level. It is shown that the consideration of the vibronic coupling mechanism is essential to establish not only a quantitative but also a qualitative profile of the GOS, as a function of the momentum transferred, for the dipole forbidden transitions (Σg+1→1Σu− and Σg+1→1Δu). For the dipole allowed Σg+→Σu+ transition, the calculated GOS is in good agreement with the available experimental data.

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Differential and integral cross sections for the valence-shell excitations in D2O studied by fast electron impact

Wang

Peng

et al. 2022

Phys. Rev. A

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Configuration interaction and relaxation effects on generalized and optical oscillator strengths of the H2O molecule: The X1A1→A1B1 transition

Cited by 3 publications

References 43 publications

Experimental and theoretical study on generalized oscillator strengths of the valence-shell electronic excitations in CF4

Experimental and theoretical study on generalized oscillator strengths of the valence-shell electronic excitations in CF4

Generalized oscillator strengths of carbon disulfide calculated by multireference configuration interaction

Differential and integral cross sections for the valence-shell excitations in D2O studied by fast electron impact

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