INVESTIGADORES
PIRO Oscar Enrique
artículos
Título:
On the Electronic Structure of Metastable Nitroprusside Ion in Na2[Fe(CN)5NO].2H2O. A Comparative Single Crystal ESR Study
Autor/es:
C. TERRILE; O. R. NASCIMENTO; I. J. MORAES; E. E. CASTELLANO; O. E. PIRO; J. A. GÜIDA; P. J. AYMONINO
Revista:
SOLID STATE COMMUNICATIONS
Editorial:
Pergamon Press
Referencias:
Año: 1990 vol. 73 p. 481 - 486
ISSN:
0038-1098
Resumen:
Laser irradiation of Na2[Fe(CN)5NO].2H20 at low temperature produces two long-living nitroprusside metastable states which, upon heating, decay at two different temperatures. In addition, laser illumination of previously X-ray irradiated crystals generates traces of the closely related [Fe(CN)5NO]2- species with linear (axial) NCFeNO geometry where the unpaired electron is localized on a dz^2 orbital as detected by ESR spectroscopy [g||=2.0055(6), g(perp)= 2.0348(4); A||=I6.9(1)G, A(perp)=14.8(1)G]. There also exists another stable form of [Fe(CN)5NO] 3- with bent FeNO group and the odd electron located in a pi*NO orbital. The comparison of metastable [Fe(CN)5NO]2- and the [Fe(CN)5NO]3- (dz^2 ) species suggests that the electronic structure of the high temperature metastable state should be described as 1B2:6e(dxx,dyz)^4 2b2(dxy)^1 5al(dz^2)^1 . This assignment is consistent with reported optical absorption, MSssbauer, Raman, and IR data.
