Table of Contents
Journal of Theoretical Chemistry
Volume 2013 (2013), Article ID 734354, 4 pages
Research Article

A Computational Determination of the Lowest Energy Electronic and Geometric States of First Row Transition Metal Dioxygen Dications

1Environmental Resource Management, 1 Beacon Street, 5th Floor, Boston, MA 02108, USA
2Department of Chemistry, Biochemistry, and Physics, Marist College, 3399 North Road, Poughkeepsie, NY 12601, USA

Received 28 March 2013; Accepted 13 August 2013

Academic Editors: G. Borosky, P. Derosa, G. Pacchioni, A. Stavrakoudis, A. Tilocca, and B. M. Wong

Copyright © 2013 Jillian Lennartz et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


The lowest energy geometric structures and electronic spin states of first row transition metal (TM) dioxygen dication molecules ([TM–O2]2+; TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) have been determined at the B3LYP/LANL2DZ level of theory (along with an extra -type polarization function added to the O atoms). In order to further verify the spin states, CASSCF(6 + , 9) energy points were determined ( = number of TM electrons). It has been found that with the exception of [Sc–O2]2+, [V–O2]2+, [Co–O2]2+, and [Ni–O2]2+, all [TM–O2]2+ molecules take on a high-spin state. [Sc–O2]2+ adopts a trigonal structure, while [Ti–O2]2+-[Mn–O2]2+ are essentially linear and [Fe–O2]2+-[Zn–O2]2+ are bent. It is further noted that the O–O bond decreases from 130.0 pm to 118.1 pm as the TM changes from Sc to Zn. However, the TM–O2 bond lengths fluctuate between values of 182.2 pm for [Ni–O2]2+ and 232.2 pm for [Zn–O2]2+.