Resonant two-photon detachment of WO2−

The Journal of Chemical Physics

Ning

et al. 2015

We report a photodetachment and high-resolution photoelectron imaging study of cold 2-hydroxyphenoxide anion, o - HO(C6H4)O(-), cooled in a cryogenic ion trap. Photodetachment spectroscopy revealed a dipole-bound state (DBS) of the anion, 25 ± 5 cm(-1), below the detachment threshold of 18 784 ± 5 cm−1 (2.3289 ± 0.0006 eV), i.e., the electron affinity of the 2-hydroxyphenoxy radical o - HO(C6H4)O(⋅). Twenty-two vibrational levels of the DBS are observed as resonances in the photodetachment spectrum. By tuning the detachment laser to these DBS vibrational levels, we obtain 22 high-resolution resonant photoelectron spectra, which are highly non-Franck-Condon due to mode-selective autodetachment and the Δv = - 1 propensity rule. Numerous Franck-Condon inactive vibrational modes are observed in the resonant photoelectron spectra, significantly expanding the vibrational information that is available in traditional high-resolution photoelectron spectroscopy. A total of 15 fundamental vibrational frequencies are obtained for the o - HO(C6H4)O(⋅) radical from both the photodetachment spectrum and the resonant photoelectron spectra, including six symmetry-forbidden out-of-plane modes as a result of resonant enhancement.

Section: B Nature and Assignment Of The Photodetachment Spectrummentioning

confidence: 86%

Section: General Comments For Vibrational Autodetachment From a DImentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Vibrational state-selective autodetachment photoelectron spectroscopy from dipole-bound states of cold 2-hydroxyphenoxide: o − HO(C6H4)O−

Huang

The Journal of Chemical Physics

Ning

et al. 2015

“…R2PD−PES of the WO 2 − anion has been reported recently via a possible spin-forbidden excited state. 10 However, the R2PD−PE spectra of WO 2 − were plagued by complex vibronic structures due to large structural changes, congested electronic states, and vibrational hot bands.…”

mentioning

confidence: 99%

Vibrational State-Selective Resonant Two-Photon Photoelectron Spectroscopy of AuS^– via a Spin-Forbidden Excited State

Huang

et al. 2015

J. Phys. Chem. Lett.

Vibrational state-selective resonant two-photon photoelectron spectra have been obtained via a triplet intermediate state ((3)Σ(-)) of AuS(-) near its detachment threshold using high-resolution photoelectron imaging of cryogenically cooled AuS(-) anions. Four vibrational levels of the (3)Σ(-) excited state are observed to be below the detachment threshold. Resonant two-photon absorptions through these levels yield vibrational state-selective photoelectron spectra to the (2)Σ final state of neutral AuS with broad and drastically different Franck-Condon distributions, reflecting the symmetries of the vibrational wave functions of the (3)Σ(-) intermediate state. The (3)Σ(-) excited state is spin-forbidden from the (1)Σ(+) ground state of AuS(-) and is accessed due to strong relativistic effects. The nature of the (3)Σ(-) excited state is confirmed by angular distributions of the photoelectron images and quantum calculations.

“…The progression would necessarily be anharmonic and perturbed by strong vibronic coupling, given the increase in spin−orbit coupling with the more linear structure sampled at higher bend quanta. 54 The VDE value for the 17 B 2 ← 16 Δ g transition is computationally identical to the energy for the analogous neutral linear state (imaginary bend frequency), which is 1.22 eV. The blue trace shows the simulation based on the hypothetical 17 Δ u ← 16 Δ g transition, which appears similar to band A.…”

Section: ■ Results and Discussionmentioning

confidence: 86%

New Photoelectron–Valence Electron Interactions Evident in the Photoelectron Spectrum of Gd₂O^–

et al. 2021

Self Cite

Evidence of strong photoelectron–valence electron (PEVE) interactions has been observed in the anion photoelectron (PE) spectra of several lanthanide suboxide clusters, which are exceptionally complex from an electronic structure standpoint and are strongly correlated systems. The PE spectrum of Gd2O–, which should have relatively simple electronic structure because of its half-filled 4f subshell, exhibits numerous electronic transitions. The electron affinity determined from the spectrum is 0.26 eV. The intensities of transitions to excited states increase relative to the lower-energy states with lower photon energy, which is consistent with shakeup transitions driven by time-dependent electron–neutral interactions. A group of intense spectral features that lie between electron binding energies of 0.7 and 2.3 eV are assigned to transitions involving detachment of an electron from outer-valence σu and σg orbitals that have large Gd 6s contributions. The spectra show parallel transition manifolds in general, which is consistent with detachment from these orbitals. However, several distinct perpendicular transitions are observed adjacent to several of the vertical transitions. A possible explanation invoking interaction between the ejected electron and the high-spin neutral is proposed. Specifically, the angular momentum of electrons ejected from σu or σg orbitals, which is = 1, can switch to = 0, 2 with an associated change in the Ms of the remnant neutral, which is spin–orbit coupling between a free electron and the spin of a neutral.