Forb_Trans.ppt.pptVIP

Complex Q’ value (in 10-4cm-1) Co(NH4)2(SO4)2?6H2O -0.2 ? 0.05 Na4CoPTS -0.2 ? 0.1 Tutton Salt (theoretical estimation) Co(BPT) 0.8 +1.60 ? 0.05 Q’ = 3e2qQ/84 and Q’’ = (e2qQ/84) (?/2) = (Q’/3) (?/2) From Q’ = 1.6 x 10-4cm-1 and Q’’ = 0.1 x 10-4cm-1, Hence asymmetry parameter, ? = 0.375 The field gradient at the nucleus can be separated into valence and lattice contributions as eq = e(1 – R) qval + e(1-??) qlig where (1 – R) and (1 - ??) are the Sternheimer antishielding factors. Qval = ? nj ?3 cos2?j - 1?3d ?rj-3 ?3d Qlig = ? ? nLi ?3cos2?Li – 1/rLi3? + ? ZL?3cos2? - 1/rL3? Q’ = (3e2 Q/84) (1 – R) ? nj ?3cos2?j - 1?3d ?rj-3?3d Double Quantum Transition and Regular Half-field Transition Involves ?ms = ?2 but it arise from the rapid consecutive absorption of two single Quanta i.e final state is reached via transition to an intermediate state. Requirement: Energy separations between the adjacent levels be equal Occurs at magnetic fields comparable to those for g = 2 However, half-field transitions (since they occur at a half field of the main ?ms = ?1 transition) Occur (in S = 1) systems when D/h? ? Usually, Bmin = 2.0023/gmin [B20/4 –(D’)2 / 3 – (E’)2]12 BDq = 2.0023/gav [(B02 – (D’)2 / 3 – (E’)2]1/2 If D/h? increases, the resonances may be off the available magnetic field, it is necessary to work at higher fields (eg) Ni (S = 1) Total transition probability for a DQ transition in a 3 level system = Pik = Pij x Pjk If D/h? increases, the resonances may be off the available magnetic field, it is necessary to work at higher fields Spin Flip Transitions Any nucleus in the environment of a unpaired spin will feel a magnectic field Be coming from the isotropic and dipolar fields. Depending on the orientation of the electron, the fields felt by the nucleus can be termed Be+ and Be- which in turn will orient with respect to the applied field. The resulting field will be along, say Bx and By, at an angle ?. The ang