Issue 29, 2022

Photoelectron spectroscopy of cryogenically cooled NiO2via slow photoelectron velocity-map imaging

Abstract

High-resolution anion photoelectron spectra of cryogenically cooled NiO2 anions, obtained using slow photoelectron velocity-map imaging (cryo-SEVI), are presented in tandem with coupled cluster electronic structure calculations including relativistic effects. The experimental spectra encompass the [X with combining tilde]1Σg+[X with combining tilde]2Πg, ã3Πg[X with combining tilde]2Πg, and Ã1Πg[X with combining tilde]2Πg photodetachment transitions of linear ONiO0/−, revealing previously unobserved vibrational structure in all three electronic bands. The high-resolution afforded by cryo-SEVI allows for the extraction of vibrational frequencies for each state, consistent with those previously measured in the ground state and in good agreement with scalar-relativistic coupled-cluster calculations. Previously unobserved vibrational structure is observed in the ã3Πg and Ã1Πg states and is tentatively assigned. Further, a refined electron affinity of 3.0464(7) eV for NiO2 is obtained as well as precise term energies for the ã and à states of NiO2 of 0.3982(7) and 0.7422(10) eV, respectively. Numerous Franck–Condon forbidden transitions involving the doubly degenerate ν2 bending mode are observed and ascribed to Herzberg-Teller coupling to an excited electronic state.

Graphical abstract: Photoelectron spectroscopy of cryogenically cooled NiO2−via slow photoelectron velocity-map imaging

Supplementary files

Article information

Article type
Paper
Submitted
27 may. 2022
Accepted
07 jul. 2022
First published
07 jul. 2022

Phys. Chem. Chem. Phys., 2022,24, 17496-17503

Author version available

Photoelectron spectroscopy of cryogenically cooled NiO2via slow photoelectron velocity-map imaging

M. C. Babin, M. DeWitt, J. A. Lau, M. L. Weichman, J. B. Kim, L. Cheng and D. M. Neumark, Phys. Chem. Chem. Phys., 2022, 24, 17496 DOI: 10.1039/D2CP02396B

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