Electronic Structures and Molecular Properties of Chalcogen Nitrides Se2N2 and SeSN2
Tuononen, H., Suontamo, R., Valkonen, J., Laitinen, R., & Chivers, T. (2005). Electronic Structures and Molecular Properties of Chalcogen Nitrides Se2N2 and SeSN2. Journal of Physical Chemistry A, 109 (28), 6309-6317. doi:10.1021/jp052502a
Published inJournal of Physical Chemistry A
DisciplineEpäorgaaninen ja analyyttinen kemia
© 2005 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
The electronic structures and molecular properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 have been studied using various ab initio and density functional methods. All molecules share a qualitatively similar electronic structure and can be primarily described as 2π-electron aromatics having minor singlet diradical character of 6−8% that can be attributed solely to the nitrogen atoms. This diradical character is manifested in the prediction of their molecular properties, in which coupled cluster and multiconfigurational approaches, as well as density functional methods, show the best performance. The conventional ab initio methods RHF and MP2 completely fail to describe these systems. Predictions for the vibrational frequencies, IR intensities, Raman activities, and 14N, 15N, and 77Se chemical shifts, as well as singlet excitation energies of Se2N2 and SeSN2, have been made. The computed high-level spectroscopic data will be of considerable value in future efforts aimed at the preparation of the conducting polymers (SeN)x and (SeNSN)x. ...