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 1A1g → 3A2g (b2g → b1g) and 1A1g → 1A2g (b2g → b1g) excitations, consistent with the calculated orbital energy ordering, b2g(xy) < eg(xz,yz) < a1g(z2) ≪ b1g(x2 − y2).
Abstract
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 1A1g → 3A2g (b2g → b1g) and 1A1g → 1A2g (b2g → b1g) excitations.