IJCRR - 5(1), January, 2013
Pages: 13-31
CORRELATION OF ELECTRON SPIN RESONANCE, NUCLEAR QUADRUPOLE RESONANCE, REFLECTANCE AND MAGNETIC PARAMETERS OF Ti (II, III), V (II, III &IV) AND Cr (III) COMPLEXES: A DFT STUDY
Author: Harminder Singh, A. K. Bhardwaj, M. L. Sehgal, Susheel K. Mittal
Category: General Sciences
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Abstract:
DFT implemented by ADF2010.02 was applied to calculate and correlate 14 ESR, NQR, reflectance and magnetic parameters of the first transition metal ion complexes. Commands like Single Point, LDA, Default, Spin Orbit, Unrestricted, None and Collinear were applied to the software using DZ or TPZ Basis sets.36 complexes such as [TiX4]- (X=F, Cl, Br, I), [TiX4]2- (X=F, Cl, I), [TiX6]3-,4- (X=F, Cl, Br I),[Ti(OH2)4]2+,3+, [VF4]0,1- (X=F, Cl, Br I), [VX6]4- (X = F, Cl, Br I), [V(H2O)6]+2, [CrX6]3- (X= F, Cl, Br, I, CN) and [Cr (NH3)]3+ having both the regular (Td, Oh) and the distorted stereochemistries (C1, D4h , D6h , D12 and S4) were selected to carry out all the computations in the gas phase. In [TiX6]4- (X= Br, I), LDA was replaced by GGABP. Spin Polarization was kept equal to the number of unpaired electrons present in the metal ions respectively. All the complexes possessed a Nysom symmetry and definite Pre-optimization .The software gave ESR (g11, g22, g33, giso, a11, a22, a33, Aten ), NQR [?, q11, q22, q33, NQCC] and optimization parameters [bonding energy, total energy having contributions from LDA and GGA components]. Two more ESR parameters [H^, ΔEhf] were calculated from these parameters. Also, two Reflectance parameters [? complex, % covalent character] were obtained from the giso parameter. Again, five magnetic parameters [?soc, ?t, ?net, t2g electron delocalization and its constant k] were derived from ESR and Reflectance parameters. Lastly, the Laplace equation was verified from the NQR parameters (q11, q22, q33,).The values of the ESR parameter like t2g electron delocalization constant (k) agreed well with the Reflectance parameter namely Nephelauxetic ratio (?35) because both determine the % covalent character in the complexes. The values of all the parameters calculated by the selective use of 18 relations would change with the change in oxidation states of the metal ions but were always in agreement with their reported values.
Keywords: DFT, Nephelauxetic ratio, Pre-optimization.
Citation:
Harminder Singh, A. K. Bhardwaj, M. L. Sehgal, Susheel K. Mittal. CORRELATION OF ELECTRON SPIN RESONANCE, NUCLEAR QUADRUPOLE RESONANCE, REFLECTANCE AND MAGNETIC PARAMETERS OF Ti (II, III), V (II, III &IV) AND Cr (III) COMPLEXES: A DFT STUDY International Journal of Current Research and Review. 5(1), January, 13-31
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