We give a detailed description of the structural, electronic and optical properties of the [M(dmit)2] (M = Ni, Pd, Pt) neutral dithiolenes by calculating their geometries, their bonding energies, their vibrational spectra, their ground and exited electronic states within the density functional approach. The dominant rela- tivistic effects are treated by using the zeroth-order regular approximation. We compare their properties with those of the similar [M(H2timdt)2 ] (M = Ni, Pd, Pt) series of dithiolenes and we find, in particular, that the LUMOs in the [M(dmit)2] compounds lay at energy very close to those of the HOMOs in the cor- responding [M(H2 tmidt)2 ] compounds, which indicates the mixed-ligand complexes as possible non-linear optical materials. The analysis of the UV–vis–NIR spectrum of the [Ni(dmit)2] complex shows that the intense NIR absorption is redshifted with respect to that in [Ni(H2timdt)2], which may candidate this compound as dyes for Q-switching and/or mode locking the NdYAG and Nd:YLF lasers.
Structural and new spectroscopic properties of neutral [M(dmit)2] (dmit = C3S52-, 1,3-dithiole-2-thione-4,5-dithiolate) and [M(H2timdt)2](H2timdt = H2C3N2S31-, monoanion of imidazolidine-2,4,5-trithione) complexes within the density functional approach
ARCA, MASSIMILIANO;
2007-01-01
Abstract
We give a detailed description of the structural, electronic and optical properties of the [M(dmit)2] (M = Ni, Pd, Pt) neutral dithiolenes by calculating their geometries, their bonding energies, their vibrational spectra, their ground and exited electronic states within the density functional approach. The dominant rela- tivistic effects are treated by using the zeroth-order regular approximation. We compare their properties with those of the similar [M(H2timdt)2 ] (M = Ni, Pd, Pt) series of dithiolenes and we find, in particular, that the LUMOs in the [M(dmit)2] compounds lay at energy very close to those of the HOMOs in the cor- responding [M(H2 tmidt)2 ] compounds, which indicates the mixed-ligand complexes as possible non-linear optical materials. The analysis of the UV–vis–NIR spectrum of the [Ni(dmit)2] complex shows that the intense NIR absorption is redshifted with respect to that in [Ni(H2timdt)2], which may candidate this compound as dyes for Q-switching and/or mode locking the NdYAG and Nd:YLF lasers.
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