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Chem Lecture Notes on DD splitting

Chem Lecture Notes on DD splitting - WW amumamwattmow...

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Unformatted text preview: WW amumamwattmow Diamagnetism ype of magnetic susceptibility Paramagnetism ' Ferromagnetism Antiferro- magnetism Sign TABLE 10.1 Approximate magnitude of x (c.g.s.) Types of magnetic behavior and their characteristics. Dependence on Ho Origin —————————————————-—————-——-—-————————-———-————_ Negative Positive Positive Positive 1 x 10‘6 0 — 1'4 Independent Independent _ 10‘2 ~— 104 Dependent i x , 0 —- 1—4. 5' v' i l May depend V Electronic charge { Angular momentum (electron spin) Ti dipole exchange N dipole exchange 5,85 Sh .ze_.. am 0855 56+ 2* . _ V afigé @6333 WE. ‘ V « o.m.m.\§o_a ¢>~m . qu . 7 ,_ “my a , . WmWNOOAZva a AZEAVNmeObwdmNO Nnncfimobvm.mmm0 ,.,. g m fic .. s .5an men > 83;“ 90 HEN 0». mmethn mm 5:089 ,. .C e. myctoUnv men m 83.3 :5 HEN 0m AZRMEOUQ mm $59.3. :5: x» a mzmwnw sommzfi. 9: man: m .82.: mm Bowsmsmawm m: :8 382: 8.5098? H" mm 33¢me 95 8 oxuonmaoifi 598593 . mg &m§mmna§ 853658: 8 90 mcmoogmczzw. . 4 . . ‘ '\ \ ‘4 The men— Femr effect The tetragonal distortions just described represent specific examples " of the Jinn-Teller effect: If the ground electronic configuration of a nonlinear molecule is degenerate, then the molecule W111 distort -so as to remove the » degeneracy and achieve a lower energy. An octahedral d9 complex is degenerate because the odd electron can occupy either the dx2_yz orbital or the dz; orbital, and a tetragonal distortion lowers the energy of the latter Distortion to square—planar, ; with the electrons paired in the d.: orbital removes the degeneracy and lowers the energy of the complex, and can be regarded as an extreme case of the Jahn—Teller effect. Note that the effect does not refer to the degeneracies of orbitals but to the degeneracies of the . electron configurations that arise when the orbitals are partially occupied. The Jahn-Teller effect identifies an unstable geometry; it does not predict the preferred distortion. The examples we have cited involve the elongation of two axial bonds and the compression of the four bonds that lie in a plane. The alternative distortion, compression along My Mm ,, “on... . ”,an ~.- ”a“, . U KGal/mole O 5 IO FIG. 5.6 Lattice energies of bivalent first row transition metal oxides, suilfiidies and seltenides, versus number of d electrons. I r. H From 933:5) ‘LnJcWLA-M t» “3““ mm: U Kcal/ mole Ti N0. ofd electrons FIG. 5.5 Lattice energies of bivalent first row transition metal halides, MX2 , as a function of the number of d electrons. From 933:5) ‘fn’frafiw’kon t. Lag-MA Imam ...
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