Article

Electronic Excited States of Tetracyanonickelate(II)

California Institute of Technology, Mail Code 139-74, Pasadena, California 91125
Inorg. Chem., 2006, 45 (18), pp 7397–7400
DOI: 10.1021/ic060584r
Publication Date (Web): August 10, 2006
Copyright © 2006 American Chemical Society

Synopsis

We revisit the assignment of the absorption spectrum of tetracyanonickelate(II) by calculating energies of excitations with time-dependent density functional theory. Our results give strong evidence that the original assignment of the spectrum is not entirely correct. We reassign bands at 22 400 and 32 300 cm-1 to the 1A1g3A2g (b2g → b1g) and 1A1g1A2g (b2g → b1g) excitations, consistent with the calculated orbital energy ordering, b2g(xy) < eg(xz,yz) < a1g(z2) ≪ b1g(x2y2).

Abstract

Abstract Image

We revisit the assignment of the absorption spectrum of tetracyanonickelate(II) by calculating energies of excitations with time-dependent density functional theory. Our results give strong evidence that the original assignment of the spectrum is only partially correct. We thus propose an alternative assignment consistent with our theoretical calculations and all available experimental evidence. In particular, we reassign the bands at 22 400 and 32 300 cm-1 to the 1A1g3A2g (b2g → b1g) and 1A1g1A2g (b2g → b1g) excitations.

Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.

Metrics

Received 6 April 2006
Published online 10 August 2006
Published in print 1 September 2006
Explore by: