Fig. 49 Latina sche wd forte ni and cron in tiene bond resent of the Valence bond (VB) theory 137 ‘The MO method is mathematically complex and is not as intuitive as VB. ‘theory, In the water molecule, iti far more convenient to think in terms of| localized O-H bonds rather than multi-centre H-~O--H interactions. Hove ‘ver, there are many compounds for which the MO approach provides more satisfying description of the bonding. In many respects, this similar the situation with bond enthalpies. As chemists, we know thatthe four CH. bonds in methane are equivalent, but as we showed in Box 44, ifthe bonds srw broken sequentially, we obtain a diferent bond enthalpy value or each step. Both the VB and MO methods are approximations for obtaining. the ‘molecular wavefunction, yXmoleeule). Both methods must approach the same tue" (molecule) and should, ultimately, give equivalent wavefunctions General overview of valence bond theory Jn valence bond theory, # description of the bonding within 8 diatomic ‘molecule is detcmined by considering the perturbation thatthe two atoms have on one another as they penetrate one another’ regions of space. In practice this means thal We attempt to woe an approximation to the “real ‘wavefunction for the molecule in terms of a combination of wavefunctions dseribing individual 2cleteon interactions. The details of the mathematics fare not relevant to our discussion * “The consideration of electrons from the start isan important characteristic of VB models ‘The bonding in H, ~ an initial approach Consider the formation of an Hs molecule. Each hydrogen atom consists of a proton and an electron. In Figure 49 the two nucei ure labelled Hy and Hy and the tw electrons are labelled I and 2. When the 10 H.atoms are well separated from one another, eeetton 1 willbe wholly associated with Hi, and electron 2 will be fully associated with Hy, Let this situation be described by the wavefunction 4 ‘Although we have given each electron a diferent label, they are actualy indistinguishable from one another. Therefore, when the atoms are close together, we eannot tell which electron is associated with which nucleus — lecizon 2 could be with Hy and electron | with Hy, Let this situation be describe by the wavefunction 9s ‘An overall desription of the system containing the two hydrogen atoms, ‘Wcovalent), can he writen in the form of equation 4.15 ‘woovalent) = 0 +0 aa) The wavefunction e(eovalent) defines an energy. When this aleulated usa function ofthe inemuclear separation H-Hy. it provides an energy minic mum of 303KImol at an internuclear distance of 87pm for Hs, Using ‘equation 4.15, therefore, dags nat give an answer in good agreement with either the experimental interauclear HH distance (74 pm) or the bond For more indepth duson, a Meeay (IPT) Coon’ Flows, de, Oto138 ——_CHAPTER4 + Homonuclear covalent bonds More about resonance structures: ee Section 7.2 = Normalization see Section 38 Jlissocation energy (436K mo!) and some refinement of the method is clearly nocd The bonding in Hy ~a refinement of the initial picture [Although we have so far allowed each of the nuclei Hy ad Hy (0 be asso~ sated with either ofthe elestrons 1 and, we should also allow fora situation jn which one or other of the nuclei might be associated with both electrons ‘There ae four situations that can areas H, and Hy comeclose together + (aucteus H, with electron 1) and (nucleus Hy with eletron 2 + (oucteus Hy with electron 2) and (nucleus Hy with electron 1 + (nucleus Hi with both electrons 1 and 2) and ¢nucleus Hig with no electrons): + (aucteus Hy with no electrons) and (nucleus My with both electrons 1 and 2). ‘While the first vo situations retain neutrality at each atomic entre, the last two desenbe the ransfer ofan electron from one nucleus to the othe. This has the effect of producing two ions, H and H~. If Hy has no electrons, Hy becomes Hy". and Hy becomes Hy”. If Ha has both electrons, Hx becomes Hy - and Hy becomes Hy’ There isan equal chance of fering [Ha- Hp*] or [M7 Hy" since the two hydrogen atoms are identical ‘The effect of allowing for contebutions from [Hy Hy] or [Hy Hy”)is to build into the valence bond model the possibilty that the wavefunction that describes the bonding region between the two hydrogen atoms may have an ionic comiburion in dition to the covalent contribution that We Ihave already described. This i represented in equation 4.16 soles ‘(covalent + fe wien] (416) ‘The coelicent c indicates the relative contribution made by the wave Funetion tion) to the overall wavefunction v{molecule). ‘With rogued 1 the Hy molec, equation 4.16 means that we should write three possible structures to represent the covalent and ionic contributions to the bonding description. Structures 47a, 4.7b and 4.7e are called resonance structures and a double-headed arrow is wsed to represent the resonance hetwoon them, ra) a (aro Is very important to realize that the purely covalent and the purely ionic forms of the Hs molecule do not exist separately. We are merely trying to describe the H, molecule by the wavefunction (molecule) in terms of eon- butions from the two extreme bonding models represented by covalent) and oioni). ‘By tying dlferent values of ¢ in equation 4.16, an estimate of the inter- nuclear distance that corresponds to the energy minimum of the system can be obvained which comes close to the experimental bond distance I the wavefunctions are normalized, a value of e025 gives an HH. internuclear distance of 75 pm, in close agreement with the experimentally determined value. The predicted bond disocistion enesgy is 398 kl mot Further mathematical refinement can greatly improve upon this value at the expense ofthe simple physieal picture() Hyerogen fuori ‘ey pont: ta byroges ture he boning ol more cect othe ato are he at Seeing ow concerted be som. ‘Aan lsat f hs eer ons one simple hetrnclea itr ol- hie HE Thee alec stale senate fer molar ob ati te a Stal of and the and pce of thre ae 127 alee rons aco ‘Sneath five wollen ecnsraed frm the ve bs cbt “Thee ele Hc ecomrctd y alonng sn sorb over ith he f2sand 2p, ortas sing the nxt an Tse the smi eta omine fo pie threo mca ofthe frm Yign eaetyiae Te proce ifs de Ep. ond Fp rts eutocnd tay bane 9 Spey ee ee talc H bal of tase. These rah ate here example tthe Nat ening ial mento eater an are mle eas ond Yo sige atom ‘Noein, bss there cen of inerson nator aoc mole Ab nt we he gu clean for molar rials igre 221 skews terrain empl gen The To iain po ont Fain hrs a decry diene bare tad te Hs al ig href coed mailto he Fat and cacy ontondag The 23 ‘aloe bonding than the Teta an both Hi ad 3p sara The 3 “tal abi nd pial ls inchs te Istana sar ik ‘Ser onpared wih he Burn orb) and ens cobs pedonnaey oe ‘Mpegs orbaug ole he "fo of hcg aloe econ ca he 20 eal forming hod worn he we azo Sirens the oad ia he to cia ars nonlonng and caine ay othe Fat Ts sensi wth be comemonal moe tee one simon the acne sam. lhe cc are ow aon he onion [ite moles 12 One npn eure ste atl hc sons py ‘Sivathr opinion Par flows tha wean the HF ce {Ste plas ws paral mn cargo the tom whch ued eprint (9 Carbon monoside ‘ey points Te wD a scxdon nonunde mote ean anos ortega ney ca ‘aon th LUMO isan anbondingoita ‘The molecular orbital enegy-tevel diagram for caybon monoxide is a somewhat more omplicaed example than HE Because oth atoms have 2s and 2p orbitals that can Jarcipate nthe formation of @ and x oral The energy-leve! agra shown Fig. 2.22, The ground state configuration 0; lotto! “The 1 onal localized moly onthe atom an hereto ese nonbonding oF weakly booing, The 26 orbals bonding The totals consti the doubly degen ‘ke pa of fonding = nial, wth manly C2p eri character The HOMO in CO se $e, which predominany C2p, in charter aly nonbonding ad lcated on the © [ton The LUMO i the doshly degenerate pa of snibonding eel, wh aay Cap orbital character (Fig. 2.23). This combination of fone orbital fl eel Taw locled on Cand a pair of empty x orbitals one reason why so many com- founds arekaowan in which CO is bonded tos dicta the called dane carbonyl, fhe HOMO lone psi orbital of CO partner nthe formation of 3 6 ood se te LUMO anbonding = orbital paris im the Formas oe bonds othe meta tos (Chapter 22. Although the deen in lectroneatity between C nd Oi lana the experiential ‘ayo the ect dipole monet of the CO molecule (0D. where Disa unit of dipole ‘moment the dbye) tama Moreover the mopar nd of the spo son the C tor ‘Epic tha being the len cisroneatve stom. Thin od sanion stems rom the fact ‘hav the lone pats and bonding pas have «complex dutnbuton ie wrang to conchde {hat Rests he bonding leans ae tainly on the O ator, O thereat ed of te ‘ipl, a hs anos the balancing eect ofthe lone pat om the C ater. The inference ‘of platy from clecuonegaivy Is parca unreable when antibonding orbital are wpe 1 i 1 ways Bee aur 221° Te naa al IS Sagn en oes ae 223° Mal i ney oS 96 5¢ Qo o te ° serie hte ct te ‘omc otal nat te magne ot a