The dependence of the spin-Hamiltonian parameters of the [Ti(OH2)6]3+ cation on the mode of water co-ordination
Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Standard
The dependence of the spin-Hamiltonian parameters of the [Ti(OH2)6]3+ cation on the mode of water co-ordination. / Carver, Graham; Bendix, Jesper; Tregenna-Piggott, Philip L.W.
I: Chemical Physics, Bind 282, Nr. 2, 01.09.2002, s. 245-263.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Harvard
APA
Vancouver
Author
Bibtex
}
RIS
TY - JOUR
T1 - The dependence of the spin-Hamiltonian parameters of the [Ti(OH2)6]3+ cation on the mode of water co-ordination
AU - Carver, Graham
AU - Bendix, Jesper
AU - Tregenna-Piggott, Philip L.W.
PY - 2002/9/1
Y1 - 2002/9/1
N2 - Single crystal X-band EPR spectra of Ti(III) doped C(NH2)3MIII(SO4)2 ·6H2O Gu[MIII:Ti]SH, MIII = GaIII, A1III) collected at ∼1.9 K, are presented. Principal g values for Gu[Ga:Ti]SH and Gu[A1:Ti]SH of g∥ ∼ 0.965, g⊥ ∼ 0, and g∥ ∼ 0.984, g⊥ ∼ 0, respectively, are derived. The values of g∥are significantly less than that previously reported for Cs[Ga:Ti]SH (g∥∼ 1.161) and this work is principally concerned with accounting for the difference. Analytical expressions are derived for the first-order Jahn-Teller coupling coefficients between the states comprising the 2Tg (Th) ground term and the twisting librations of the coordinating water molecules, in the framework of the Angular Overlap Model (AOM); and, values of g∥ computed by numerical diagonalisation of the vibronic Hamiltonian. On the basis of differences in the mode of water co-ordination alone, g∥is calculated to increase from 0.965 (Gu[Ga:Ti]SH) to ∼1.10 (Cs[Ga:Ti]SH), in fair agreement with experiment. The EPR spectra of Gu[Ga:Ti]SH contain well-resolved proton superhyperfine structure. The magnitude of the superhyperfine coupling constant far exceeds that inferred from the EPR spectrum of Cs[Ga:Ti]SH, and this too is rationalised in terms of the different stereochemistries of the [Ti(OH2)6]3+ cation in the two crystal systems.
AB - Single crystal X-band EPR spectra of Ti(III) doped C(NH2)3MIII(SO4)2 ·6H2O Gu[MIII:Ti]SH, MIII = GaIII, A1III) collected at ∼1.9 K, are presented. Principal g values for Gu[Ga:Ti]SH and Gu[A1:Ti]SH of g∥ ∼ 0.965, g⊥ ∼ 0, and g∥ ∼ 0.984, g⊥ ∼ 0, respectively, are derived. The values of g∥are significantly less than that previously reported for Cs[Ga:Ti]SH (g∥∼ 1.161) and this work is principally concerned with accounting for the difference. Analytical expressions are derived for the first-order Jahn-Teller coupling coefficients between the states comprising the 2Tg (Th) ground term and the twisting librations of the coordinating water molecules, in the framework of the Angular Overlap Model (AOM); and, values of g∥ computed by numerical diagonalisation of the vibronic Hamiltonian. On the basis of differences in the mode of water co-ordination alone, g∥is calculated to increase from 0.965 (Gu[Ga:Ti]SH) to ∼1.10 (Cs[Ga:Ti]SH), in fair agreement with experiment. The EPR spectra of Gu[Ga:Ti]SH contain well-resolved proton superhyperfine structure. The magnitude of the superhyperfine coupling constant far exceeds that inferred from the EPR spectrum of Cs[Ga:Ti]SH, and this too is rationalised in terms of the different stereochemistries of the [Ti(OH2)6]3+ cation in the two crystal systems.
UR - http://www.scopus.com/inward/record.url?scp=0036724768&partnerID=8YFLogxK
U2 - 10.1016/S0301-0104(02)00678-X
DO - 10.1016/S0301-0104(02)00678-X
M3 - Journal article
AN - SCOPUS:0036724768
VL - 282
SP - 245
EP - 263
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
IS - 2
ER -
ID: 240003257