PERE) 005 cctons in motscuis: ptatomios Fig. 5.41 On the lft are shown the contributions which each AO snakes tothe MOs forthe p orbitals in a line constructed using the same graphical method as was sed for four orbitals. The Ix MO {s bonding across ll the atoms, but the 2r MO is nonbonding since the middle AO makes no contribution (he sine wave is 20 at this point). The 3x MO is antibonding. On the right is shown the occupation ofthe MOs for the aly anion and cation, i ot ° anpeaten y-PXp-PS,, i 4 it jain Cx CR, smramen yen tS 4 = oe + -- anion cation ‘The ally cation and anion The allyl cation and anion, illustrated opposite, are somewhat exotic looking species but which have nevertheless been studied both in solution and in the solid state. Both species can be thought of as deriving from propene: removing H? from this molecule gives the ally! anion, and removing H™ gives the allyl cation, although a more realistic reaction would be by the loss of Br~ from allyl bromide (CH,=CHCH,Br). The experimental evidence is that both of these molecules are planar and symmetrical, in the sense that the two end carbons are the same, The localized structures shown opposite make it seem as if the end carbons are different, as one is doubly bonded, and the other is only singly bonded. We will show in this section that these ions have a delocalized x system which accounts for the symmetry, and also explains several other properties of the molecules. ‘The allyl anion has eighteen valence electrons: four from each of the three carbons, five from the hydrogens and one for the negative charge. If we imagine that the carbons are sp? hybridized, and then use these hybrids to form the two C-C and five C-H o bonds, this accounts for fourteen of the electrons, leaving. four to go into the r MOs. For the allyl cation there are two fewer electrons, leaving just two to go into the system. Each carbon has an out-of-plane 2p AO, and these interact to form the MOs. As before, we can model these using three orbitals in a row, and can construct the form of the MOs using the same graphical argument as we used before ‘The contributions of the AOs to the MOs is shown on the left of Fig, 5.41. [As before, we have added an imaginary atom to the left and to the right of the three atoms, and then inscribed one, two and three half sine waves across these five positions. The 1x MO is bonding across all atoms, but the AO from the central atom makes a larger contribution to the MO than do the AOs on the end atoms. ‘The 2x MO has one node, which is spaced by (N+ I/(n+ 1) x= (4/2) xR = 2. from the fictitious atom on the left. This places the node on the central atom, so the AO from this atom makes no contribution. The AOs from the end atoms make equal, and opposite, contributions. This MO is nonbonding as the two |AOs on the end atoms are too far apart for there to be a significant interaction between them. ‘The 3x MO has two nodes which are spaced by (N-+1)/(n+ 1)xR = (4/3)xR = 1.333. So there are nodes at 1.333 R and 2.667 8 from the fictitious atom on theleft. The contribution from each AO is in the opposite sense to its neighbours, so all the interactions are antibonding. As before, the energy of the MOs increase as the number of nodes increases. In the ally anion, there are four electrons in the x system so these occupy the Ix and 2r MOs. The occupation of the 2 MO makes no contribution to the bonding, so x bonding is entirely due to the 1x MO. Since the two electrons in this MO are spread across all three atoms, so we have a partial x bond between adjacent atoms. We note that the Lr MO is symmetric, so the bonding likewise has to be symmetric, in contrast to the impression given by the localized picture. Although the two electrons in 2x MO do not contribute to the bonding, they do increase the electron density on the end atoms. A full MO calculation shows. that there is a partial (negative) charge of ~0.62 on the end atoms, with slight positive charges on all the other atoms. This can be compared to ethene in which there is a charge of -0.35 on each carbon, and +0.17 in each hydrogen. In the allyl anion, there is clearly a concentration of negative charge on the end carbon atoms In the cation, only the 1 MO is occupied, so again there isa partial x bond across all three atoms. ‘The form of this MO tells us that the electron density will be greatest on the central atom, in contrast to the anion where the density is greatest on the end atoms. 5.8.2 Resonance structures [As we have seen, the delocalized picture of the bonding in butadiene and in the allyl cation and anion gives a picture which is in accord with experimental evi- dence about these molecules, whereas the localized picture does not. However, ‘we can improve on the localized picture somewhat by introducing the concept of resonance, which was introduced briefly in section 1.1.4 on page 7. How this applies to the molecules we have been discussing so far is illustrated in Fig. 5.42 on the following page. Ally! cation and anion In Fig, 5.42 (a) two localized bonding structures are given for the allyl cation, ‘one with the positive charge on the right-most carbon, and one with the charge (on the left-most carbon. ‘These two structures are entirely equivalent, and are both equally acceptable, However, as we have seen, neither of these structures on their own is adequate to explain the observed properties of the cation, because they do not show that the two end carbons are the same. ‘The idea of resonance is that if we take these two structures together, they are-a better representation of what is going on than either on its own. It is important not to get the wrong idea here. We are not saying that the molecule is flicking back and forth between these two structures. What we are saying is that the true electronic structure is best represented by a mixture of these two. So, the x bond is neither located on the left nor on the right, but across all three atoms. Similarly, the positive charge is not localized, but is spread out. ‘These different localized representations of the bonding are called resonance structures, and traditionally they are connected by a double-headed arrow. In different resonance structures the atoms are all in the same positions, but the electrons (ie. the bonds) are arranged differently. So these resonance structures are different representations of the same molecule. Figure 5.42 (b) and (c) on the next page show two commonly used alternative ‘ways of representing the delocalized bonding in the allyl cation. In (b) a dashed line is used to represent the idea that the x bond is spread over all three 58 Delocalized bondingChapler 5 teres in maces: peyatoies Fig. 6.42 Mlustration of different ways of presenting delocalized = ‘bonding In a) we see 0 resonance sruetures ofthe ally cation, connected bya double headed azrow. These are to equivalent localized representations ofthe bonding, but neither i adequate on its own, Shown in (b) and (c) are akernative ways of representing the bonding: a dashed line indicates a delocalized bond, and the (4 represents a possible location ofthe postive charge in ‘one ofthe resonance structures ‘The equivalent representations of the allyl anion are shown in (€)-{8). Benzene can be eepresnted as resonance struetutes, shown in (gh onthe ways shown in (h) and). oH 2 oa \ <> Heo 4 allyl cation atoms, and the positive charge is shown as being associated with the whole molecule, Representation (c) also uses a dashed line, but the positions at which the positive charge may be localized, as shown by the resonance structures in (a), are indicated as ‘(+)’. The purpose of the bracket around the plus sign is to remind us that a full positive charge is not present, but that this is a position at which a positive charge is present in one resonance structure. Structure (c) is more useful than (b) as the former shows the possible locations of the positive charge. Figure 5.42 (d) shows the resonance structures of the allyl anion, and further alternative representations are shown in (e) and (f). These are closely analogous to those used for the allyl cation. Finally, (g) gives the resonance structures for benzene, which differ in the placement of the double bonds. This delocalized bonding is often represented in the ways shown in (h) and (i). But Butadiene is rather a different case to benzene and the allyl ions. The delocalized picture tells us that there is a partial x bond between the two central carbons, 0 if we are to use the resonance concept to explain this then we need to include some resonance structures in which there is a double bond between the middle two carbons, Figure 5.43 on the next page shows two such resonance structures, A and C, along with the usual form, B, What is significantly different about structures A and C is that in order to place the double bond in the middle we have had to create a positive charge on one of the end carbons, and a negative charge on the other. Structures A and C only differ in the placement of these ‘two charges. For benzene and the allyl ions, the two resonance structures contribute ‘equally i.e. the electronic arrangement is a 50:50 mixture of the two. However, for butadiene the central double bond is only partial, so A and C are only minor contributors to the structure, whereas B is the major contributor. There must be ‘equal contributions from A and C as otherwise we predict the molecule to have a net dipole moment, which it certainly does not.5.9 Delocalized structures including heteroatoms ry tt tt Brg ng ae Pala Sx peenOeH Ho *B We Se Oe we a ¢ i - ‘ 8 ° Fig. 5.43 Mlustation of resonance for butadiene. The usual representation, B falls to account forthe partial x bond between the central carbons, bu thiscan be remedied by including small contributions from forms & and C. ‘The concept of resonance has to be used with great care. It is especially important to understand that the resonance structures are just different localized representations of the bonding, and that the true electronic structure is repre- sented by some combination of these resonance structures: most emphatically the molecule does not ‘flicker’ between these resonance structures. We have a tendency to want to represent the bonding in molecules using localized ‘two-centre two-electron bonds, simply as this is both familiar and convenient. However, we have to accept that such representations are, for many molecules, neither accurate nor adequate. The MO picture avoids all of these difficulties as it naturally produces a delocalized picture of bonding. ‘The concept of resonance is a way of trying to introduce delocalized bonding, using localized structures. 5.9 Delocalized structure: \cluding heteroatoms So far we have only considered delocalized structures in which all of the atoms are the same (carbon). However, much the same considerations apply when there is a mixture of carbon and heteroatoms (nitrogen, oxygen). The MOs we have developed for orbitals in a line will not be quite right as the constituent AOs will not all have the same energy, but as we shall see these MOs are still a useful guide. 5.9.1 Carboxylate anion At the start of this section we used the carboxylate ion, whose structure is shown in Fig, 5.36 on page 167, as an example of a delocalized bonding. You will recall that both C-O bond lengths in such an ion are the same, and intermediate between those for double and single bonds. Using the concept of resonance, wwe can rationalise this observation by proposing that there are two equally contributing resonance structures, as shown opposite. ‘An alternative explanation is to use an MO description of the system. If wwe allow the carbon and both of the oxygens to be sp? hybridized, then each has a 2p orbital pointing out of the plane. These three AOs will combine to form three x MOs, in which we have to accommodate four electrons ~ one from each atom, plus one for the negative charge. ‘To a rough approximation we can model this « system as three 2p orbitals in a line, and so can use the MOs illustrated in Fig. 5.41 on page 172. ‘Two of the electrons occupy the Lz MO, which is bonding across all atoms, and two occupy the nonbonding 2x MO, which localizes electron density on the end atoms. This is of course just the same description that we used for the allyl Figure 5.44 on the following page shows the computed form of the occupied MO in the methanoate anion (HCO5). These agree well with the simple MOs ° e ? -f and ‘ » carbonate anion © Weotnk 5.9 View, and rotate in realtime, iso-urface representations of the threes MOs ofthe ‘mthanoate ion illustrated in Fig. 5.44PEE) ces cxcvore in moe: pats Homo -3 ° ° i i Ax, Stinat, 0 g i hatin ° Cd Hot wH Ub eet ae Hoos Hw oH 1 I 4 A A 8 Fig, 5:45 A base may remove H* from the carbon adjacent to. carbonyl group to give an enolate ‘anion, Two resonance forms ofthe enolate are shown: in A, the negative charge i onthe carbon, and in Bit ison the oxygen, © weblink 5.10 View, and rotate in real time, iso-surface representations of the thrce x MOs of the enolate ion (from ethanal illustrated in Fig. 5:46. HOMO LUMO Fig. 5.44 Iso-surface pls ofthe computed form ofthe x MOs inthe methanoate anion (HCOS the hydrogen atom is coming towards us. The HOMO and LUMO compare well withthe form ofthe 2x and 3x MOs predicted in Fig. 541 on page 1725 the lowest energy x MO, labelled HOMO-3, compares well withthe Lr MO. computed for three p orbitals in a line. Given that the pair of electrons in MO1 is responsible for the bonding across all three atoms, what we have is a partial bond between the C and each O. Often this is represented by a dashed line, in the way shown opposite. 5.9.2 Enolates If we take a ketone or an aldehyde and treat it with a strong base, itis possible to ionize one of the hydrogens on the carbon adjacent to the carbonyl carbon to give what is known as an enolate. The process is illustrated in Fig, 5.45 for ethanal, The two carbons and the oxygen lie in a plane, so just as in the allyl anion and the carboxylate anion there is the possibility of forming a delocalized system involving these three atoms. We can model this using the simple MO from Fig. 5.41 on page 172, placing two electrons in the It MO and two in the 2x MO. There is thus partial x bonding across all three atoms. However, this enolate lacks the symmetry of the carboxylate anion, so we must expect the actual x MOs to look somewhat different from those shown in Fig, 5.41 Figure 5.46 on the next page shows the computed form of the occupied x MOs for the enolate anion from ethanal. ‘The lowest energy x MO, labelled HOMO-2, compares well with the Iz MO in Fig. 5.41. However, rather than the orbitals from all three atoms contributing equally, as they do in the 1x MO, the orbitals from the oxygen atom and the carbonyl carbon are the major contributors. The next highest energy x MO is also the HOMO; broadly speaking this is analogous to the 2 MO from Fig. 5.41. However, in contrast to the 2x MO, there is a contribution from the carbonyl carbon, and the contributions from the other carbon and the oxygen are not the same. When we come to look at the reactions of this enolate, we will see that the form of the HOMO iis important in determining how this species reacts. ‘The enolate can also be described using the two resonance structures A and B shown in Fig. 5.45. Both of these forms are significant contributors, as is indicated by a detailed MO calculation which shows that the partial charges are ~0.81 on the oxygen, +0.34 on the carbonyl carbon, and ~0,62 on the other carbonHOMO -2 HOMO Fig. 5.46 Io-surface plots ofthe computed form of then MOS in the enolate formed from ethanal structure shown in Fig. 5.45 on the facing page). The CH: group i to the lft and the carbonyl aygen ist the right. 5.9.3 Amides Amides, such as methanamide (shown opposite), have a rather unexpected struc tural feature which is illustrated in Fig. 5.47. This shows the three-dimensional structure of the amide obtained by X-ray diffraction on a crystal. The special hing to note is that the oxygen, the two carbon atoms, the nitrogen and the two hydrogens attached to it all le in a plane. At first sight this is unexpected. ‘The nitrogen has three single bonds and a lone pair, so we would expect the bonds to be arranged in a trigonal pyramid, lust as they are in NHs, or in an amine RNH>. ‘Whar is going on here becomes clear once we look at the form of the x MOs of methanamide (HCONHz) shown in Fig, 5.48 on the following page. These slearly show that there isan interaction between 2p AOs on the nitrogen, carbon and oxygen. In particular, the lowest energy x MO (HOMO-2) shows that there ‘a significane bonding interaction across all three of these atoms. We could describe this situation by saying that the nitrogen is approximately sp? hybridized, which makes available an out-of-plane 2p AO which can then be involved in x interactions with 2p AOs on the carbon and the oxygen. The overlap of these 2p AOs is optimized when they all point in the same direction, and this accounts for the planarity of the molecule. These orbitals indicate that there is a partial x bond between the nitrogen and the carbon. In terms of resonance structures, this can be accommodated by saying that there is some contribution from the resonance structure B shown opposite. Further evidence that there is a partial bond between the N and the C comes from spectroscopic measurements which indicate that the energy barrier for rotation about the C-N bond is around 70 kJ mol”, significantly higher than that expected for a single bond. In energetic terms, we can rationalize this planar geometry of the amide by noting that by adopting this geometry the x system can be extended over three atoms. The most bonding x MO spread over the three atoms is lower in energy han the C-O bonding MO, thus by forming the localized system the energy of the molecule as a whole is lowered. 3.10 Moving on Between this chapter and the previous one we have shown how molecular orbitals can be used to describe the bonding in molecules. Although the detailed ‘orm and energies of the MOs can only be found from a computer calculation, 5.10 Moving on Lumo Fig. 547 Three-dimensional structure of methanamide obtained by Xeray diffraction. Note tha all ‘ofthe atoms le in a plane, ° oe fH eH eye Saye! I Hoy H H A 8 © Weblink 5.11 View, and rotate in realtime, iso-surface representations of the three MOs of smethanamide illustrated in Fig. 5.48,Bonding in solids Key points + In solids, the overlap between orbitals on different atoms can give rise to crystal ‘orbitals which extend throughout the material; these orbitals are analogous to delo- calized MOs. «+ The crystal orbitals which arise from a particular set of atomic orbitals form a band, which can hold a certain number of electrons. «+ The electrical conductivity of metals is the result of partially filed bands; insulators have full bands, but in semiconductors there is a small gap between a filled and an empty band, ‘* The lattice enthalpy of an ionic solid can be estimated using a simple electrostatic model. + The lattice enthalpy depends on the size (radii) of the ions and their three- dimensional arrangement in the crystal. In section 1.6 on page 25 we discussed briefly how different types of solids could be distinguished on the basis of the bonding they contain. These types are: ‘+ molecular solids, which contain discrete molecules, held together by weak interactions, such as hydrogen bonds; ‘giant covalent solids, in which there is a network of covalent bonds extending throughout the entice structure; # metallic solids, in which there is extensive delocalization of the electrons; * ionic solids, in which it is the interactions between discrete ions w1 hold the structure together. Now that we have developed the molecular orbital approach, we are in a position to be more precise about the nature of the bonding in metals and in giant covalent structures. We will see that such structures can be deseribed using the concept of bands which are rather like giant molecular orbitals which extend throughout the material. Having done this, we will turn our attention to ionic solids, and show how a simple electrostatic model can account for energetics of such structures. ‘An important question which arises in these discussions is why a given chemical species adopts a particular form. For example, why is it that under normal conditions we find lithium as the solid metal, but nitrogen as No gas? Ics, as we have seen, perfectly possible for lithium to form the molecule Lis,HRY oes crore ici but it must be that the metallic form is preferred as it is ‘more stable’. Similarly, although we could conceive of a metallic form of nitrogen, the molecular form is ‘more stable’. Precisely what we mean by ‘more stable’ will have to wait until the next chapter when we look at the topic of chemical thermodynamics. For the moment we will not enquire as to why a particular form is preferred, but simply content ourselves with describing the bonding in a given structure. 6.1 Metallic bonding: introducing bands A defining feature of metals is that they are excellent conductors of electricity, which we take to imply that they contain electrons which are free to move throughout the solid. So, rather than electrons being closely associated with a particular nucleus, they are free to move from atom to atom. “This description of the behaviour of electrons in a metal is reminiscent of our discussion of delocalized molecular orbitals, particularly those from extended x systems described in section 5.8 on page 167. We saw there that an electron occupying an MO in such a system is not localized on one or two atoms, but is spread out over all of the atoms whose AOs contribute to the MO. The picture we will develop of a metal is that some of the electrons occupy orbitals which are delocalized throughout the entire structure. These orbitals are formed in just the same way as MOs, but instead of being derived from a few AOs, they are formed from AOs on every atom in the whole solid. These orbitals, which extend throughout the entire structure, lead to what are known as bands, whose properties we can use to describe metallic bonding. We will start by considering a one-dimensional band, which is the easiest to visualize, and then generalize this to more dimensions. 6.1.1 Bands in one dimension Let us start by imagining a chain of lithium atoms, and the molecular orbitals they might give rise to. As we did when thinking about discrete molecules, we can ignore the two 1s orbitals as these are so contracted that they are unlikely to overlap with other orbitals. The 1s? are the core electrons. What we are left with is a single (valence) electron in the 2s AO on each atom. ‘The MOs formed from a chain of 2s AOs can be constructed in exactly the same way as was described in section 5.8.1 on page 168 for a chain of 2p orbitals. Figure 6.1 on the next page shows the resulting MOs for chains of between two and eleven atoms. The MOs are placed vertically according to their energies. In each case, the lowest energy MO is one in which there is constructive interference between all the constituent AOs i.e. the AOs all have the same sign. The highest energy MO is when there is destructive interference between adjacent AOs ie. the signs alternate. From the diagram it can be seen that as, the number of atoms increases, the energy range which the MOs span increases at first but then starts to level out, so that the energy of the most bonding MO becomes independent of the number of atoms in the chain, ‘The same is true of the most antibonding MO. The reason for this is that, for a chain of N atoms, in the most bonding MO there are (NW ~1) bonding interactions between AQs on adjacent atoms. The total number of bonding interactions per atom in the chain is therefore (N-1)/N, and in the limit that the number of atoms is large, this ratio becomes one. As a6:1 Metalic bonding: introducing bands . ie Oe ah wets ‘numberof atoms in chain result, for chains with many atoms, the number of bonding interactions per atom is independent of the number of atoms, and therefore the energy of the most bonding MO is independent of the number of atoms. A similar argument applies to the most antibonding MO, in which the number of antibonding interactions per atom tends to one for large N. We also note that for four or more atoms, the MOs are not evenly spread across the energy range, but tend to cluster at the top and bottom of the range. This point is made even more clearly in Fig, 6.2 which shows the energy levels for a chain of 200 atoms. As we approach the lowest and highest energies, the levels become more and more densely packed, to the point where the separation between levels is no longer clear from the diagram. A convenient way of describing the way in which the levels are spread out is to define a quantity known as the density of states. This is the number of energy levels in a small range of energies centred around a particular energy. As is shown in Fig. 6.2, for this chain the density of states is quite low in the middle of the energy range, but increases sharply at the highest and lowest energies. In a macroscopic sample of a metal, there will not be twenty or 200 atoms in the chain, but more like 10®° atoms. Nevertheless, the pattern of the energies of the resulting MOs will be of the same form as we have described: they will cover a certain energy range, which is independent of the number of atoms, and. there will be a clustering of the MOs at the extremities of this energy range. As these MOs encompass the whole sample, they are usually called crystal orbitals (COs). The COs which result from the overlap of a particular AO form what is called a band. The band has a width which is the energy separation between the lowest energy CO and the highest energy CO. ‘A useful way of thinking about the formation of a band is to imagine a thought experiment in which we start out with a large separation between the atoms in our chain, At such large separations there is no interaction between the AOs, and so each of the NV AOs is unaffected by being in the chain. There are thus N energy levels, but they are all the same. AAs the atoms are moved closer together, the orbitals start to interact, giving rise to COs with a range of energies, from the most bonding to the most antibonding. In other words, a band is formed. The closer the atoms become, the stronger the interaction between the AOs, and so the most bonding CO drops further in energy, and the most antibonding CO goes up further in energy ice. as is illustrated in Fig. 6.3 on the following page, the width of the band Fig. 6.1 Representation of the form of the MOs, and their energies, for 2-11 s orbitals in a ow. The lowest energy MO has constructive overlap herween all adjacent AOs, whereas in the highest energy MO there is destructive overlap between adjacent AOs. Asthe number of ‘orbitals increases the energy range between the lowest and highest energy MO tends rowards a constant value, and the MOs cluster towards the ends of this range. Seto Fg.6:2On the let shown the serge ofthe MOs for 200 atoms ina chain, On the right shown the density of states which ithe numberof energy levels ina small range of energies. Note how the ders of sates increases dramatically a we approach the lowest or highest energies.fiz ‘Chapter 6 Bonding in solids increases. The width of the band therefore reflects the strength of the interaction between the AOs. Of course, if the atoms get too close together repulsive interactions will start to come into play, and the width of the band will stop inereasing or may even decrease, Just as with a molecule, there will be a separation at which the optimum interaction occurs. energy —+ In the case of a chain of N lithium atoms, each atom contributes one electron B to the band: there are thus N electrons to be accommodated in the band. The decreasing band itself contains N COs, as the number of COs must be the same as the aan + number of AOs. As with MOs, two electrons can occupy each CO, so half iimeract the COs are occupied, starting from the lowest energy and working up to the non-bonding level in the middle of the band. We therefore predict that the energy is lowered when the chain of atoms comes together, as this results in a lowering in the energy of the electrons as decreases ie as the interaction they occupy bonding COs. It should be remembered that the COs cluster at the berween the As increases. The lower energy end of the band, so the majority of the electrons are in COs with COs inthe bottom half ofthe a significant bonding character. band are bonding, while those in thesor tal acansbondie "6.1.2 Conduction of electricity Fig. 63 Illustration of how the width of a band initially ineceases ‘asthe separation between the AOS airs sea One of the key features of a metal is its ability to conduct electricity, and the ‘mporane andthe band willsese Concept of a band gives us a ready explanation for this phenomenon. The key 7 ideas ilsrared in Fig. 64 forthe two cases ofa partly filed band anda filed Let us start by considering the case of a partly filled band, shown in the upper part of the diagram. In (a) we see, in schematic form, the levels which comprise the band in three different parts of the sample; the electrons are shown as green dots. Of course in practice there would be vastly more COs in the band, and, many more electrons, but these few levels shown here will suffice. Fig. 64 llustration of ow a ply lod bad ha wo [na ‘conduction. In (a) we see ‘snap # ) shot’ ofthe COs from a band at thre different locations inthe sample electrons are shown in sreen. Applying an electric fed Teads to shift inthe energies of the COs, as shown in () Electrons can then flow frm let to tight by dropping down into lower enery unoccupied COs, as shown by the arrows in (c). The material is therefore a conductor. If the bands ate full, as shown in @ « — (6 no such Now is possible as J there are no empty COs onthe right forthe electrons to move HHll HHI HH HHH ttt ttt ttt ttt tH ttt HTH energy +++ + +When an electric field is applied, as shown in (b), the electrons close to the negative end are raised in energy, and those close to the positive end are lowered inenergy. We can think of this as leading to a change in the energies of the COs, as shown in (b). The result of applying the field is that the energies of the COs within the band vary across the sample. ‘With the field applied, there are now empty COs on the right of the sample which are Jower in energy than filled COs on the left. Some electrons can therefore drop down into lower energy COs, as shown by the arrows in (c), hus effectively moving from left to right across the sample. This flow of electrons across the sample results in an electric current, so the sample is therefore a conductor of electricity. ‘Now consider the case where the band is full, shown in the lower part of the diagram. Just as before, applying an electric field shifts the energies of the COs to those shown in (e). However, as there are no empty COs on the right-hand side, there are no spaces for the electrons to flow into. Thus there is no current, and the sample does not therefore conduct electricity. We come to the very important conclusion that to conduct electricity a sample must have a partially filed band. The picture shown in Fig. 6.4 on the facing page is slightly deceiving as the COs extend throughout the sample rather than being localised as shown. In practice the effect of the electric field is to cause the energy of the COs to vary continuously across the sample. So, what we have in this figure is ‘snap shots? of the COs at three different parts of the sample, | 6.1 Metalic bonding: introducing bands I I Selt-test 6.1 Conduction of electricity ‘Would you expect an empty band to contribute to the conduction of electric- ity? Would a band one-third filled with electrons conduct electricity more or less effectively than a one-quarter filled band? 6.1.3 Bands in three dimensions Although we have introduced the concept of a band by thinking, about a one- dimensional chain of atoms, you can see in principle how the same idea can be extended to three dimensions. The AOs on each atom interact with those on all of the neighbouring atoms, giving rise to COs which extend in all directions through the solid, Just as in the one-dimensional case, the interaction of the ‘AOs leads to the formation of bands which contain COs ranging from strongly bonding to strongly antibonding. ‘The detailed form of the bands depends on the exact three-dimensional arrangement of the atoms in the solid. As a result, the width of the band can be different in different directions in the solid, Overall, the behaviour of the bands in three dimensions is rather a complex matter, which is well beyond the scope of this text. Overlapping bands In the previous section, we considered the case of a chain of lithium atoms, and showed that the 2s AOs give rise to a band which is half full. This predicts that there is net bonding, and that there will be conduction along the chain. Moving to three dimensions does not really alter this picture in a significant way. The overlap of N AOs gives rise to a band containing V COs, whichcaper sondg inst band @ © i Fig. 65 Illustration ofthe consequences of two bands ‘overlapping. In (a) we sce a full s band (shaded blue) overlapping ‘with an empty p band. The energy ‘of the electrons is decreased if some move from the top of the + band tothe bottom of the p band, as shown in (b) Since the electrons have moved from antibonding COs to bonding COs, the steength of the bonding is increase. ‘sband vary between strongly bonding and strongly antibonding. Each lithium atom contributes one electzon, so the band is half full, which explains why the metallic solid is lower in energy than the gaseous atoms, and also why the material is a conductor. ‘Moving to beryllium, which has the configuration 2s*, the same kind of band arises but this time there is a total of 2N electrons from N atoms, so the band is completely filled. This means that for every bonding CO that is occupied, an equivalent antibonding CO is also occupied. Asa result we predict that there is no reduction in energy when the gaseous atoms form a solid. Furthermore, as the band is full, we do not expect the sample to conduct elect ‘These predictions are, of course, complerely wrong. ‘The stable form of beryllium under normal conditions is a metalic solid, which in fact has a higher enthalpy of vaporization than does lithium (324 kJ mol” as compared to 159 kJ mol"); in addition, beryllium is an excellent conductor of electricity. In fact, what is going on here is that in addition to the band formed from the 2s AOs, there is another band formed from the overlap of the 2p AOs. This should come as no surprise, since we have seen in simple molecules that MOs are formed from the overlap of all the available AOs. If this p band overlaps the s band, as shown in Fig, 6.5 (a), then the strength of bonding can be increased if some of the electrons at the fop of the s band are transferred into the bottom of the p band, as shown in (b). The reason why this increases the strength of bonding is that the electrons from the top of the s band will be coming from antibonding COs and going into bonding COs which are at the bottom of the p band. Therefore, we can rationalize the observation that beryllium is a metallic solid by supposing that there is a p band which overlaps in this way, thus allowing for there to be more bonding electrons than antibonding ones. This also results in partially filled bands which account for the high conductivity. Just as with MOs, the details of the bands, such as their energies and widths, and whether or not they will overlap, are not something that we can predict from simple considerations. ‘Therefore, we will be using bands to rationalize observations rather than make predictions. For example, in the case of beryllium we conclude that the p band must overlap the s band, but there is no simple way of predicting that this will be so, or the extent of the overlap. 6.1.4 Bands formed from MOs Bands can be formed from the overlap of other kinds of orbitals than As, and in many cases this is a more natural way to approach the problem. Ina metal, the atom is the fundamental object which repeats throughout the whole sample, but in other solids the repeating unit may consist of more than one atom. A simple example of this is the case of solid hydrogen, which consists of discrete H; molecules. The repeating motif is therefore the hydrogen molecule, not a hydrogen atom. Given this, it is natural to form bands from the MOs of Hp, rather than the AOs on H. Just as with lithium, itis easiest to start out thinking about a linear chain of hydrogen molecules, and the one-dimensional bands that the orbitals from these molecules form. The process is visualized in Fig. 6.6 on the facing page. First, look at the upper part of the diagram, which is for the case that the spacing between the Hz molecules is large compared to the H-H bond length. A band is formed from the Hz o bonding MOs, and a separate band is formed from the o* antibonding MOs. For each of these bands, the COs with the lowest and highest energy are shown schematically.