465 . 8 s 5 c) C) ©) | p Ww 2 Pp SS | Qe © 7 CH) - Faure 10.2 : Overlap of valence orbitals to give MOs in the second period (no s-p mixing). The contour diagrams ae the results of calculations for No. [Adapted from W. L. Jorgensen and L. Salem, The Organic ‘Chemiss's Book of Orbitals, Academic, New York, 1973; p. 79.] __ The doubly degenerate (2p,, 2p,) set of orbitals give positive overlap as seen in Figure 10.2(e) to produce the familiar x bonding orbitals (i.e., the degenerate pair of my and x, bonds). These orbitals have the symmetry of the Il, irreducible representation, $0 they are properly labeled as x, bonding MOs. There is also a corresponding de- Generate antibonding set of orbitals resulting from negative overlap; these have the Symmetry of the II, irreducible representation, so they are properly labeled as my" ‘antibonding MOs.aN Chapter $0.) MOLFCAN AR Omer, SowTo, The electron configurations of these lection configurations load to preeiet Os, 20.0, 1 Sand Os? 10 Hond energies ¢ increase along thie acquence The strongest and she 7 phon energy atsout MORIInOL trom date yn Table TE LOr ome 7 plist» bog Ibond length in bond energy for 0)" should be abeyp S70 mol! OM ' for a single 7 band iatomics can be predicted ws in «af bond orders as follows O,? Hl dec tener ‘Umravioiet and Visible Spectra Flectrone can he promoted from full ‘or partiay fll) ortitals to vacant for partially vacent) orbitals by photons of fight as previcags ixcussed in Section & 4 The lowest energy absorp wally OCCUTS 10 the visthle « ultraviolet (UV) region of the spectrum, and results in the promotion of an elector from the HOMO to the LUMO of the molecule or ion. The diatomic halogen mole cules 1 through 1. have a x“! HOMO and aa,°° LUMO. The intense color of sey molecules 1s duc to the absorption of light while an electron is being. proms ted fron the HOMO to the LUMO. Since overlap and bond strength fall down a grup of ty penody table as the orbitals become more diffuse (Section 3.1, Table 10.2. the sepa ration of the HOMO and the LUMO decrease from F; through I; As we shal! see 9 Chapte: 12. Fs virtually colorless since this absorption oveurs in the UV region the spectrum, C1, 1s yellow since the absorption band spans some of the UV and som: of the adjacent visible region, Br; is deep red since the band is clearly in the visible, | 2% purple since the band is at even lower energy in the visible region. ‘Tate 10.2 Bond Energies and Lengths of Some Homonuclear Diatomic Molecules and loas* Bont Bond Bead oo teres, Leet tare a . et) Molecaie ' ~ a 238 m » an ie Me” 20 ow oO, = oe, ~ = o » ut o ow Pe w “ = ms ew nn ion ae Wee a : 7 n aaa = Densmis Laeie tran BS Land aand HW Gane) Bonds Bosna A We OPW eB ot date Kat distin Cosnage | aad 1402. Bond Enerples and Lengths, Spectroscopy, and Orbital Mixing in HomonuclearDiatomc Molecules ° g i Pe = i i a é 7 ots ‘Atomic number Figure 10.6 ‘Valence orbital potential energies. [Adapted from G. L. Miessler and D. A. Tarr, Inorganic Chemistry, Prentice-Hall, Englewood Cliffs, NJ, 1991; p. 137,] The intensity of the light absorption (and color of the compound) is restricted by the symmetries of the MO being vacated in the ground stare and the one being occupied by the promoted electron in the excited state of the molecule. In order for the wave of light (which can be thought of as similar in symmetry to a x, y, or z vector, and therefore ungerade) to be absorbed, either the HOMO or the LUMO (but not both) ‘must be ungerade if the molecule possesses an inversion center. (You will recall that the weak d-d absorptions of transition metal complexes discussed in Chapter 8 for octa- hedral complexes were from the set of d orbitals labeled 12, to the set labéled ey. These absorptions are weak because both orbital sets are gerade.) In the case of the diatomic halogen molecules, the absorptions (and the colors) are intense because the HOMO is ‘gerade while the LUMO is ungerade. Mixing of Molecular Orbitals of the Same Symmetry Type. In Section 10.1 we selected our linear combinations of atomic orbitals for construction of MOs based on three criteria, which included that the atomic orbitals be of comparable energy, and that the resulting MOs have the symmetry of one of the irreducible representations. These criteria do not actually exclude some possibilities that we have ignored so far. ‘Atoms from the p, d, and f blocks have more than one type of valence orbital, and the energies of these different types of valence orbitals are often rather close, particularly at the beginning of a block, as shown by the valence orbital (potential) energies tabulated in Table 10.1 and graphed in Figure 10.6. Consequently, when we formed the o,(2s) orbital for a second-period diatomic (Fig. 10.3), we did not consider the possibility that not only the 2s but also the 2p, orbitals of the two atoms would contribute to this % molecular orbital A corollary of these criteria is that if two MOs falling in the same irreducible rep- ‘esentation have energies close to each other (i,¢., are formed from atomic orbitals with 471472 Oc (PH) C600 | 4 (-)0 o(-) ow ae"(28, P) O000-° OO ou"(28. Pi) Figure 107 Mixing or hybridization of MOs of the same symmetry type and similar energies. (2) Positive and (# negative combinations of o4(25) with ¢,(2p-) molecular orbitals; (c, a) positive and negate combinations of o,"(25) with o,°(2p.) molecular orbitals. energies close to each other), they will interact with each other (j.e., undergo a type % electron configuration interaction, orbital mixing, or “hybridization"). The 2s ortitas tare the parents of the ¢,(2s) molecular orbital, and the 2p orbitals are the parents the o,/2p) molecular orbital. But these MO's are close in energy to cach other. 3% they both belong to the same symmetry type, a. Consequently the actual MOs each partly derived from the 2s and partly derived from the 2p atomic orbitals: u(2s, p;) = ex25(A) 4 cp2s(B) + da2p,(A) + dx2p,(B) (10.10) to this ° 9 hybridized” wave function, although cq ~ ew and dy ~ dy by the eae meee mgt (4 7h Ih » ona re somewhat emphasize int howe and the p orbitals, being higher in ene | oun me Highly eonphasiced inthe ghee a in energy to start with, are tis perhaps so-viow this * ‘ ‘ epmolitules utils ew this “hybridizition" process as one of meing the ceria aay wah each ther. cnn two MO, wish nse ts oF 1 The Lowes enigy ocean He 88H he two ow sbralzet! MOS (FE ay either one, hence the vor an energy thas , which shows a single bond and three unshared electron pairs per F atom? The “guidelines of translation” are as follows: 1. Electron pairs in bonding MOs in diatomic molecules correspond to individual bonds of the indicated type (c, x, and 6). 2. When both a bonding MO and an antibonding MO of the same symmetry type (eg., and 0°) and atomic parentage are occupied by two electrons, their combined effect is to cancel each other's bonding contributions, and act as two unshared electron airs, one on each atom. 3. When an electron pair occupies a nonbonding MO in.a homonuclear diatomic molecule, it corresponds to one unshared electron pair located equally on each atom. & = that can only be represented in valence bond theory by drawing resonance ybrids, For example, the F; molecule has four elec MOs and three it antibonding MOs, which of course results in a bond order of one: a single bond: THe three pairs in antibonding MOs cancel out three pairs found in the corresponding YTS of bonding MO, so these together account for the six unshared electron paits it th Lewis structure of F2. There is no discrepane ce bond ' is antibonding (7°) by adding two electrons to the Lewis structure of :0=6:, to give [:0-G:|?, which has a lower bond order (one Jess x bond) than Oz. By subtracting electrons from the Lewis structure and then rearranging to give the best possible structure of the electron-depleted substance, one ‘can also surmise whether the HOMO is bonding or antibonding. The HOMO of O> is x’, since removing its two electrons generates (:O=O: :/2*, with one more x bond than Os. (The degeneracy of the HOMO and LUMO, so that both are SOMOs, is not revealed by this process.) 475Carbon Monoxide. This important ligand molecule is isoelectronic with No, so it has the same number of valence electrons and an energy level diagram that is related to that of N2 (Fig. 10.8), but with the significant difference that the parent atoms are not identical. Therefore they have different valence orbital energies. The same sequence of MOs does occur, however, as shown in Figure 10.11, without the gerade and ungerade labels, of course. Once again the possibility of s-p hybridization of the four a molec- ular orbitals derived from the four atomic orbitals 2s(C), 2p.(C), 2s(O), and 2p.(O) exists and actually occurs, By far, the lowest in energy of these four parent atomic orbitals is 2s(0); the lowest a hybridized MO, although hybridized, emphasizes this(a) o © Figure 10.11 Carbon monoxide (CO): (a) contours of MOs; (b) energy-level diagram; (c) photoelectron spectrum. The diagram is not to scale in that the 2s atomic orbital of oxygen and the o”*(2s) molecular orbitals are much lower in energy than shown. (a) Reprinted with permission from W. L. Jorgensen and L Salem, The Organic Chemists's Book of Orbitals, Academic Press, San Diego, 1973, p. 78: (c) adapted with permission from L. Gardner and J. A. R. Samson, Journal of Chemical Phys 1447 (1975). Copyright 1975 American Institute of Physics. 62, Parent orbital in its composition, as indicated in the contour drawing at the left of Figure 10.11. The highest energy o* molecular orbital is strongly antibonding and emphasizes the highest energy parent atomic orbital, 2p,(C). The intermediate-energy 9” and the intermediate-cnergy 7 molecular orbitals both have reduced overlap between Ha C and O atoms and therefore tend in the direction of being nonbonding. Recall the same thing happened in the case of Nz. The HOMO is the intermediate-energy 479 140 160 20.0 Ey