Theoretical and infrared spectroscopic investigation of the O2−∙benzene and O4−∙benzene complexes

Schneider, Holger; Weber, J. Mathias; Myshakin, Evgeniy M.; Jordan, Kenneth D.; Bopp, Joseph; Herden, Tobias; Johnson, Mark A.

doi:doi:10.1063/1.2759929

Volume/Page
Keyword
DOI
Citation
Advanced

Volume: Page/Article:

Search Content Type

article doi:

Citation:

Electronic and quantum dynamical insight into the ultrafast proton transfer of 1-hydroxy-2-acetonaphthone

The ultrafast proton-transfer dynamics of 1-hydroxy-2-acetonaphthone has been theoretically analyzed in the ground and first singlet excited electronic states by density functional theory calculations and quantum dynamics. The potential energies obtained in the ground electronic state reveal that the proton-transfer process does not lead to a stable keto tautomer unless the transfer of the hydrogen from the enol form is accompanied by an internal rotation of the newly formed O–H bond. Calculati...

Experimental determination of the ionization potentials of the first five members of the nanodiamond series

The ionization potentials of size- and isomer-selected diamondoids (nanodiamond containing one to five crystal cages) have been measured by means of total-ion-yield spectroscopy. We find a monotonic decrease of the ionization potential with increasing diamondoid size. This experimental result is compared to recent theoretical predictions and comparable investigations on related carbon clusters, the fullerenes, which show isomer effects to be stronger than size dependence.

The infrared spectra of the O2−∙benzene and O4−∙benzene complexes are determined by means of Ar predissociation spectroscopy. Several transitions due to CH stretch fundamentals and various combination bands are observed in the 2700–3100 cm⁻¹ region. The experimental results are interpreted with the aid of electronic structure calculations. A comparison of the calculated and experimental spectra reveals that the spectrum of O2−∙benzene most likely arises from an isomer where the superoxide molecule binds preferentially to one CH group of benzene. In contrast, the spectrum of O4−∙benzene yields a CH pattern remarkably similar to that displayed by the C_2ν X⁻∙benzene (X = halogen) complexes, consistent with a structure with two CH groups equally involved in the bonding. The lower energy vibrational fundamental transitions of the O4− anion are recovered with a slight redshift in the O4−∙benzene spectrum, establishing that this charge-delocalized dimer ion retains its identity upon complexation.

Article Outline

INTRODUCTION
METHODOLOGY
1. Experiments
2. Calculations
RESULTS AND DISCUSSION
1. Spectra of O2−∙Bz
2. Spectra of O4−∙Bz
CONCLUSIONS

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

infrared spectra, isomerism, molecular electronic states, negative ions, organic compounds, oxygen, predissociation, vibrational states

PACS

33.20.Ea

Infrared spectra
33.20.Tp

Vibrational analysis
33.15.Bh

General molecular conformation and symmetry; stereochemistry

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.2759929

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

For access to citing articles, you need to log in.

Figures (5) Tables (2)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)