Document Type

Article

Original Publication Date

2001

Journal/Book/Conference Title

The Journal of Chemical Physics

Volume

115

Issue

17

DOI of Original Publication

10.1063/1.1405438

Comments

Originally published at http://dx.doi.org/10.1063/1.1405438

Date of Submission

October 2015

Abstract

The electronic structure of CrO−n and CrOn (n=1–5) was investigated using anion photoelectron spectroscopy and density functional theory. Photoelectron spectra of CrO−n were obtained at several photon energies and yielded electron affinities, vibrational and electronic structure information about the neutral CrOn species. Density functional theory calculations were carried out for both the neutrals and anions and were used to interpret the experimental spectra. Several low-lying electronic states of CrO were observed and assigned from photodetachment of the CrO− ground state(6∑+) and an excited state (4∏), which is only 0.1 eV higher. The main spectral features of CrO−2 were interpreted based on a C2v CrO−2 (4B1). A very weak Cr(O2)− isomer was also observed with lower electron binding energies. Relatively simple and vibrationally resolved spectra were observed for CrO−3, which was determined to be D3h. The CrO3 neutral was calculated to be C3v with the Cr atom slightly out of the plane of the three O atoms. The spectrum of CrO−4 revealed a very high electron binding energy. Several isomers of CrO−4 were predicted and the ground state has a distorted tetrahedral structure (C2) without any O–O bonding. Only one stable structure was predicted forCrO−5 with a superoxo O2 bonded to a C3v CrO3.

Rights

Gutsev, G. L., Jena, P., Zhai, H. J., et al. Electronic structure of chromium oxides, CrO n − and CrO n (n=1–5) from photoelectron spectroscopy and density functional theory calculations. The Journal of Chemical Physics 115, 7935 (2001). Copyright © 2001 AIP Publishing LLC.

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