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5.04 Principles of Inorganic Chemistry II ��
Fall 2008

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e. on F(θ. Daniel G.04. Hence.5. SML εσ = EM SML 2 = β ′ SML ΔEML 2 2 εσ * = EL SML 2 = β SML ΔEML 2 2 where β and β´are constants. S(r) is invariant.04. Thus by determining the overlap integral. and therefore the overlap integral. εσ = EM SML ΔEML 2 2 εσ * = EL SML ΔEML 2 2 Note that EM. EL and ΔEML in the above expressions are constants.φ). i. Principles of Inorganic Chemistry II Prof. SML = S(r) F(θ. Under the condition of a fixed M-L distance.. Nocera Lecture 14: Angular Overlap Method (AOM) for ML for MLn Ligand Fields The Wolfsberg-Hemholtz approximation (Lecture 10) provided the LCAO-MO energy between metal and ligand to be. will depend only on the angular dependence. the energies of the MOs may be ascertained relative to the metal and ligand atomic orbitals. the overlap integral is also factored into a radial and angular product. provides a measure of SML and hence MO energy levels. SML. Daniel G. The Angular Overlap Method (AOM). Principles of Inorganic Chemistry II Prof. 5.φ) Analyzing S(r) as a function of the M–L internuclear distance. In AOM. the MO within the Wolfsberg-Hemholtz framework scales directly with the overlap integral. Nocera Lecture 14 Page 1 of 8 . SML.

Daniel G.04. Principles of Inorganic Chemistry II Prof.Because the σ orbital is symmetric. the other orbitals take on the angular dependence of the central metal orbital.73º 45 0 0 45 90 0 0 90 5. Hence. Similarly. for a dyz-orbital dz2-orbital cos sin L l ) l ) 3cos2 –1 L F( F( 54. of the overlap integral mirrors the angular dependence of the central orbital. Nocera Lecture 14 Page 2 of 8 . the angular dependence of a σ orbital as it angularly rotates about a p-orbital reflects the cos θ angular dependence of the p-orbital.φ). Hence. p-orbital …is defined angularly by a cos θ function. the angular dependence. F(θ.

π and δ ligand orbital symmetries. the interaction is defined as. For orbitals of π and δ symmetry. at θ = 0 (see above) is set equal to 1. There are three types of overlap interactions based on σ.04. This energy is defined as eσ. 2 E⎛ σ ⎜ dz2 ⎞ ⎟ = SML ⎝ ⎠ ( ) = β • F (θ . and the energies are eπ and eδ. the same holds…maximum overlap is set equal to 1. hence dz2 is destablized by eσ (the corresponding L orbital is stabilized by (β’)2 • 1 = eσ’). φ ) = β • 1 2 σ = eσ The energy for maximum overlap. Nocera Lecture 14 Page 3 of 8 . Daniel G. E dyz = E dxz = SML π = eπ ( ) ( ) 2 () 2 E dxy = E ⎛ ⎜ dx 2 − y 2 ⎞ ⎟ = S ML δ = e δ ⎝ ⎠ ( ) () 5. Principles of Inorganic Chemistry II Prof. let’s determine the energy of the d-orbitals for a M-L diatomic defined by the following coordinate system. For a σ orbital. respectively.ML Diatomic Complexes To begin. The metal orbital bears the antibonding interaction.

the SML(δ) overlap integral and associated energy is not included in most AOM treatments. 5. SML(δ) is small compared to SML(π) or SML(σ). The power of AOM is that the eσ and eπ (and eδ). there is more than 1 ligand in a typical coordination compound. the overall energy level diagrams for a M-L diatomic molecule for the three ligand classes are: ML6 Octahedral Complexes Of course. For these reasons. there are few ligands with δ orbital symmetry (if they exist. Moreover. with the only difference being an energy of stabilization of eδ for the Lδ orbital and the energy of de-stabilization of eδ for the δ metal-based orbitals. Returning to the problem at hand.04.As with the σ interaction. whereas the Lπ ligands are stabilized by eπ. the (M-Lπ)* interaction for the d-orbitals is de-stabilizing and the metal-based orbital is destablized by eπ. Daniel G. the MO energy levels of coordination compounds are determined by simply summing eσ and eπ for each M(d)-L interaction. Nocera Lecture 14 Page 4 of 8 . Principles of Inorganic Chemistry II Prof. The same case occurs for a ligand possessing a δ orbital. energies are additive. the δ symmetry arises from the pπ-systems of organic ligands). Thus.

eσ and eπ (and eδ) may be normalized to 1.φ) SML (σ and π) = 1 Note. We can imagine placing the ligand on the metal z axis (with x and y axes of M and L also aligned) and then rotate it on the surface of a sphere (thus maintaining M-L distance) to its final coordinate position. Daniel G. Nocera .04.Consider a ligand positioned arbritrarily about the metal. Within the reference frame of the ligand. SML in complex related by a coordinate transformation F (θ. Principles of Inorganic Chemistry II Prof. the coordinate transformation lines up the ligand of interest on the z axis so that the normalized energies. The transformation matrix for the coordinate transformation is: z22 z2 yz xz xy x2–y2 y2z2 x2z2 − 3 sin 2θ 2 x2y2 0 –cosφ sinθ sinφ sinθ cos2φ cosθ –sin2φ cosθ x22–y22 3 1 − cos 2θ 4 1 − sin φ sin 2θ 2 1 − cos φ sin 2θ 2 1 1 + 3 cos 2θ 4 ( ) 0 cosφ cosθ –sinφ cosθ ( ) 3 sin φ sin 2θ 2 3 cos φ sin 2θ 2 3 sin 2φ 1 − cos 2θ 4 3 cos 2φ 1 − cos 2θ 4 sinφ cos2θ cosφ cos2θ ( ) ) cos2φ sinθ –sin2φ sinθ ( 1 sin 2φ sin 2θ 2 1 cos 2φ sin 2θ 2 1 sin 2φ 3 + cos 2θ 4 1 cos 2φ 3 + cos 2θ 4 Lecture 14 Page 5 of 8 ( ) ) ( 5.

φ = 2 ( ) 1 3 1 3 dz 2 + dx 2 − y 2 = eσ + eδ 2 2 2 4 4 4 4 Visually. Recall that energy of the orbital is defined by the square of the overlap integral. Thus the above coefficients are squared to give the energy of the dz2 orbital as a result of its interaction with Ligand 2 to be. dz22. one finds. has a contribution from dz2 and dx2–y2. a σ ligand residing on the z-axis (of energy eσ) is overlapping with dz2. Daniel G. The normalized energy for L2 is its overlap with the coordinate transformed dz22: 5. E⎛ ⎜ dz2 ⎞ ⎟ ⎠ ⎝ L2 = SML σ 2 ()= β • Fσ θ . By substituting the θ = 90 and φ = 0 for Ligand 2 into the above transformation matrix. the contribution of the overlap of Ligand 2 with each metal orbital must be considered. In the coordinate transformation. Ligand θ φ 1 0 0 2 90 0 3 90 90 4 90 180 5 90 270 6 180° 0 Consider the overlap of Ligand 2 in the transformed coordinate space. for dz2 for L2 dz2 = = 1 1 + 3 cos 2θ dz 2 + 0dy2z2 − 2 4 − ( ) 3 sin2θ dx2z2 + 0dx2y2 + 2 3 d 2 2 2 x2 − y2 3 1 − cos 2θ dx 2 − y 2 2 2 4 ( ) 1 d 2 + 0dy2z2 + 0dx2z2 + 0dx2y2 + 2 z2 Thus the dz2 orbital in the transformed coordinate. This orbital interaction is given by the transformation matrix above.For ligands in an octahedral complex. the θ and φ for the six ligands values are. this result is logical.04. This is the energy for L1. Nocera Lecture 14 Page 6 of 8 . Principles of Inorganic Chemistry II Prof.

only the L2 ligand has been treated. ( ) E dxy = eπ . which is a linear combination of z2–x2 and z2–y2. The elements of the transformation matrices for these ligands are. then it will have an energy of ¾ eδ. Principles of Inorganic Chemistry II Prof. hence ¼ eσ. The transformation properties of the other d-orbitals. as they pertain to L2 orbital overlap.Note. ( ) 3 1 E⎛ ⎜ dx2 − y2 ⎞ ⎟ = eσ + eδ ⎠ 4 ⎝ 4 Until this point. L2. the dz2 orbital is actually 2z2–x2–y2. Since it is ½ the electron density of that on the z-axis.04. may be ascertained by completing the transformation matrix for θ = 90 and φ = 0.. the square of the coefficient) on the σ-axis. ( ) E dxz = eπ . The δ component of the transformation comes from the 2z2–(x2+y2) orbital functional form. Nocera Lecture 14 Page 7 of 8 .e. is looking at the x2 contribution of the wavefunction to σ bonding. E dyz = eδ . as compared to L1. Thus in the coordinate transformed system. it is ¼ the energy (i. ⎡ − 1 0 ⎡ d 2 ⎤ ⎡ d 2 ⎤ 0 0 3 ⎤ z2 ⎢ 2 2 ⎥ ⎢ ⎥ ⎢ z ⎥ ⎢ 0 0 0 − 1 0 ⎥ ⎢ dy2z2 ⎥ ⎢ dyz ⎥ ⎥⎢ ⎥ ⎢ d ⎥ = ⎢ 0 0 − 1 0 0 ⎥ ⎢ dx2z2 ⎥ ⎢ ⎢ xz ⎥ ⎢ 0 1 ⎢ dxy ⎥ 0 0 0 ⎥ ⎢ dx2y2 ⎥ ⎢ 3 ⎥⎢ ⎥ ⎢d ⎥ 2 2 0 0 1 ⎥ ⎢dx22 − y22 ⎥ ⎢2 0 ⎢ 2 ⎣ x − y ⎥ ⎦ ⎣ ⎦ ⎣ ⎦ The energy contribution from L2 to the d-orbital levels as defined by AOM is. The overlap of the d-orbitals with the other five ligands also needs to be determined. ⎡1 ⎢ ⎢0 L1 : ⎢0 ⎢ ⎢0 ⎢ ⎣0 0 0 0 0⎤ ⎥ 1 0 0 0⎥ 0 1 0 0⎥ ⎥ 0 0 1 0⎥ 0 0 0 1⎥ ⎦ ⎡ – 1 0 ⎢ 2 ⎢ 0 0 ⎢ L 5 : ⎢ 0 0 ⎢ 0 –1 ⎢ 3 − 0 ⎢ ⎣ 2 0 1 ⎡ – 1 0 0 0 3 ⎤ 2 ⎥ ⎢ 2 ⎢ 0 0 – 1 0 0 ⎥ ⎢ ⎥ L 3 : ⎢ 0 0 0 1 0 ⎥ ⎢ 0 –1 0 0 0 ⎥ ⎢ 3 ⎥ − 0 0 0 – 1 ⎥ ⎢ 2 ⎦ ⎣ 2 0 0 3 ⎤ 2 ⎥ ⎡ –1 ⎢ 2 ⎢ 0 ⎢ L 4 : ⎢ 0 ⎢ 0 ⎢ 3 ⎢ ⎣ 2 0 0 0 0 0 1 0 ⎥ ⎥ 0 1 0 0 ⎥ 1 0 0 0 ⎥ ⎥ 0 0 0 1 ⎥ 2 ⎦ 3 ⎤ 2 ⎥ ⎥ 0 ⎥ 0 – 1 0 ⎥ ⎥ 0 0 0 1⎥ 0 0 – ⎥ 2 ⎦ ⎡1 0 0 0 ⎢ 0 ⎢0 – 1 0 ⎢ L 6 : 0 0 1 0 ⎢ 0 0 –1 ⎢0 ⎢0 0 0 0 ⎣ ⎤ 0 ⎥ 0 ⎥ ⎥ 0 ⎥ 0 ⎥ ⎥ 1 ⎦ 5. Thus if L2 has an orbital of δ symmetry. Daniel G.

Principles of Inorganic Chemistry II Prof. eδ << eσ or eπ… thus eδ may be ignored. The Oh energy level diagram is: Note the d-orbital splitting is the same result obtained from the crystal field theory (CFT) model taught in freshman chemistry. L1 E(dz2) E(dyz) E(dxz) E(dxy) E(dx2–y2) L2 L3 L4 L5 L6 ETOTAL eσ eπ eπ eδ eδ 3 1 eσ + eδ 4 4 eδ eπ eπ 3 1 eσ + eδ 4 4 eπ eδ eπ 3 1 eσ + eδ 4 4 eδ eπ eπ 3 1 eσ + eδ 4 4 eπ eδ eπ eσ eπ eπ eδ eδ = 3eσ + 3eδ = 4eπ + 2eδ = 4eπ + 2eδ = 4eπ + 2eδ = 3eσ + 3eδ 3 1 eσ + eδ 4 4 3 1 eσ + eδ 4 4 3 1 eσ + eδ 4 4 3 1 eσ + eδ 4 4 As mentioned above.04.Squaring the coefficients for each of the ligands and then summing the total energy of each d-orbital. In fact the energy parameterization scales directly between CFT and AOM 10 Dq = Δ0 = 3eσ – 4eπ 5. Nocera Lecture 14 Page 8 of 8 . Daniel G.

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