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Crystal Field Splitting and Factors Affecting.

CHEM

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Bhavesh Garg
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280 views

Crystal Field Splitting and Factors Affecting.

CHEM

Uploaded by

Bhavesh Garg
Copyright
© © All Rights Reserved
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Scanned with CamScanner put) of Metal-Ligand Bonding in Complex Compounds 143 1. eg set of orbitals: d+ and d,1_,2 orbitals. This set consists of the orbitals which have lobes along the axes and hence are called axial orbitals. Quite obviously these are d,2 and orbitals. Group theory calls these e, orbitals in which e refers to doubly degenerate set. 2. by set of orbitals: dy d,., d,, orbitals. This set includes the orbitals whose lobes lie the axes and are called non-axial orbitals. Group theory calls these t,, orbitals wherein to triply degenerate set. ee T as applied to octahedral complexes: Crystal field splitting of d-orbitals in ‘complexes z rounded by six ligands which reside at the of the octahedron as shown in Fig, 18. The three axes, viz. x-, y-, and z-axes whi int along the comers have also been shown. Now suppose both the ligands on each of three axes are allowed to approach towards Bee hee MitaGrom both Revere RG (papi: resid wv thrdk metal thins Peeriis process the Clecirons tn. oxlial Ro. Mitjand aixligandsith'aia an octalieis) metal cation are repelled by negative point complex, itge or by the negative end of the dipole of ligands. (Remember CFT regards the ionic ligands as negative point charges and neutral S as dipoles), This repulsion will raise the energy of all the five d-orbitals. If all the s approaching the central cation are at an equal distance from each of the d-orbitals (i igand field is spherically symmetrical), the energy of ‘each of five d-orbitals will raise by same amount, i.e., all the d-orbitals will still remain degenerate, although they will have higher energy than before. This is only a*hyporherical situation. Since the lobes of the io e, orbitals (i.e., dz and d,*_ orbitals) lie directly in the path of the approachinging ands, the electrons in these orbitals experience greater force of repulsion than those in Wee t2, orbitals (i.e., dyy dy, and d,, orbitals) whose lobes are directed in space between path of the approaching ligands i.e., the energy of e, orbitals is increased while that the is decreased (Remember : greater is the repulsion, greater the increase in energy). IS We find that under the influence of approaching ligands, the five d-orbitals which were iginally degenerate in the free metallic cation are now split (or resolved) into two levels bs Iag level which is triply degenerate and is of lower energy, and e, level which is doubly enerate and is of higher energy (see Fig. 5.19). In other words the degeneracy of the ye d-orbitals is removed under the influence of the ligands. The separation of five d-orbitals the metal ion into two sets having different energies is called crystal field splitting or 1g) level spliting. This concept of crystal field spliting makes the basis of CFT. ‘The energy gap between fy, and e, sets is denoted br Aolorl10Dg hese in. indicates octahedral arrangement of the ligands round the central'metal cation. This energy difference && because of the difference in electrostatic field exerted by the Tigands on hg and e, sets corbitals-of the-centrat-metal cation, Ay or 10Dq is called crystal field splitting energy. With help of simple geometry it can be’ he orbitals is-U4 Ay (= 4Dq) s than that of hypothetical degenerate d-orbitals (No splitting”staie shown by dotied line in 9) and, hence, that of @, orbit ‘65 (= 6Dq) above that of the hypothetical degenerate orbitals. Thus, we find that fy set loses an energy equal to 0.4 Ay (= 4Dq) while e, set gains energy equal to 0.6 Ap (= 6Dq). In Fig 5.19 the loss and gain in energies of, and e, Scanned with CamScanner Scanned with CamScanner Scanned with CamScanner Scanned with CamScanner Scanned with CamScanner Scanned with CamScanner Scanned with CamScanner

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