fete Ror tatlRKaa lout Relea iatThe Quantum mechanical description of Lewis electron pair bond is known as Valance Bond Theory. It was developed by Heitler and London in 1927 and later extended by Pauling and Slater in 1931. The main postulates of this theory are: a. Covalent bond between two atoms is formed by the partial overlap of atomic orbitals. b. Each overlapping orbital should have one electron with opposite spin for the formation of covalent bond or one overlapping orbital should have a pair of electron & other overlapping orbital should be empty. QD Ds @®] cose CD CO- CMO gma bond & Pi bond. Covalent bonds are of two type viz..d. Sigma bond (« bond): itis the bond formed by the head on overlapping of orbitals ie. Overlapping of orbitals along molecular axis or internuclear axis. Suppose ‘2’ is molecular or internuclear axis then various sigma bonds can be formed as:- (i) s-ssigma bond: - (for example H), Lis) Qh De —* +O. ness (ii) sp sigma bond: - (for example HF, H20) De XO Dre en (iii) p-p sigma bond (for example F;, N,Q)... etc) OD DO -ODOD:1s 2p Hyorogen fuoride, HF e. _ Pibond (rt bond):- The bond formed by the lateral overlapping of atomic orbitals is, called Pi bond. This overlapping takes place on the axis perpendicular to molecular axis. If‘z' is. molecular axis then rt bond forms either on ‘y’ axis or on ‘x’ axis. Various types of pi bonds are shown below.This kind of pi bond is called pr ~pn bond, orbitals, orbitals can also form nt bonds with‘d’ & ‘p” > 2 tpn dxbond) 2 (dr-dx bond with two > S lobes interaction) >. 2 (dn- px bond with four lobes interaction) (Note: - pr- pr bond with four lobe interaction is called delta bond 5-bond) Sigma bond is stronger bond than pi because in sigma bond overlapping area of orbitals, is large in comparison to Pi-bond.(overlapping area) XE (Garge overlapping area) (Gmnall overlapping area) (8) Following overlapping of atomic orbitals is different than bond formation is not possible. > If the wave function of two overlapping atomic orbitals is different than bond formation is not possible. $35 8 8- SR — CSD C<-2 —= to bona formation CD CD — #C ‘s' orbital does not form m bond. (not possible) (h) Strength of o bonds: - Higher is the extent of overlap, higher will be the strength pop sp 88 (Descending order of strength) For example: F2 can be supposed to be formed by two ways(A) (8) F (ground stare) F (ground state) HH GT) 1 omto a 2 oF pF Bees sate Oe) iz oS Oo oom FF F — F (p-p obond) ® te FOF (e-sebend) 2s 2s Out of Aand 8, former has more probability than later because in (A) p-p o bond formation occurs which is more stable than s-s 6 bond of (B).‘Strength of x— bond: - Strength of x bond depends on the closeness of overlapping orbitals. Stablityofx bond 2pr~2pn (More stable) 3pr—2pr (More stable) 1/ (distance between overlapping orbitals) > 3pr-3pn (Less stable) > 3dn-2pn (Less stable) This is the reason that compounds with 2pn-2pn bonds are much abundant while compounds with 3pn- 2pm bonds are rareLets us discuss the structure of some molecules by the help of V.8.T. 2p om 9 2» 2pSS It is very clear from above two examples, it is evident that in between two atoms c bond forms only one time, rest all bonds are x bonds. Bo = 1 (One sigma bond) BO = 2 (One sigma + one pi bond) BO = 3 (One sigma + two pi bond) Directional characteristics of Covalent Bonds: - The valance bond theory introduced an idea about the directional property of covalent bond. For example, in water oxygen contains two lone pair, out of which one is present in 2s orbital and second lone pair is present in 2p orbital. Rest two p orbitals possess one unpaired electron which can form two sigma bonds with two hydrogen atoms. Since, all the p orbitals are mutually perpendicular to ‘one another hence the two sigma bonds (O-H Bonds) in water should be perpendicular to each other. (fet f 2 2p" i Lone pairs can form s-p sigma bond with two hydrogen atomsserbia (0 - H bond pairs are at 90° a pocbita {angular shape) TH] YAN can form s-p sigma bond with three hydrogen atoms ince, the ewo orbitals of oxygen are at right angle to each other so an angle of $0”s expected between two sigma bonds but actual bond angle observed is 104.5°. similarly expected bord angle between two sigma bonds in ammonia should be 90° but actual bond angle observed is 107°. The reason behind this deviation is explained in details in chapter 4.)ce wee ® (Molecular Orbita Orbital Theory @) oa “os e> NE 0 ‘ oa -& Sh He Ore Vv How do atoms form covalent bonds in order to form molecules? The Lewis model, which describes how atoms attain a complete octet by sharing electrons, tells us only part of the story. A drawback of the ‘model is that it treats electrons like particles and does not take into account their wavelike properties. This theory was proposed by Robert Mullikan and he explained the paramagnetic behavior of 0, which is diamagnetic according to valance bond theory. ‘Molecular orbital (MO) theory combines the tendency of atoms to fill their octets by sharing electrons (the Lewis model) with their wavelike properties—assigning electrons to a volume of space called an orbital. According to MO theory, covalent bonds result from the combination of atomic orbitals to form molecular orbitals— orbitals that belong to the whole molecule rather than to a single atom. Like an atomic orbital that describes the volume of space around the nucleus of an atom where an electron is likely to be found, a molecular orbital describes the volume of space around a molecule where an electron is likely to be found. Like atomic orbitals, molecular orbitals have specific sizes, shapes, and energies. 3Based on this, it can be concluded that electrons behaving as waves can interact with each other and the process is called interference. ‘As in waves, two types of interferences are possible: (1)’constructive and (24 Destructive. In molecules the atomic orbitals of all the atoms are assumed to interfere with each other in the form of waves and depending on the nature of interferences, two molecular orbitals result. The one which results from constructive interference is called bonding molecular orbital (BMO) and the one which results from destructive interference is called anti-bonding molecular orbital (ABMO). Obviously anti bonding MO is of higher energy than Bonding MO. In Molecular Orbital Theory (MOT) the atoms in a molecule are supposed to loose their individual control over the electrons. The nuclei of the bonded atoms are considered to be present at equilibrium inter-nuclear positions. The orbitals where the probability of finding the electrons is maximum are multicentred orbitals called molecular orbitals extending over two or more nuclei. ‘As mentioned above, when a pair of atomic orbitals combine they give rise to a pair of molecular orbitals, the bonding and the anti-bonding. The number of molecular orbitals produced must always be equal to the number of atomic orbitals involved. Electron density is increased for the bonding MO’s in the inter-nuclear region but decreased for the anti-bonding MO’s, SI 1g of the nuclei by increased electron density in bonding MO’s reduces inter nuclei repulsion and thus stabilizes the molecule whereas lower electron density even as compared to the individual atom in anti-bonding MO’s increases the repulsion and destabilizes the system.In ABMO there is one nodal plane bisecting perpendicularly the internuclear axis. BMO stabilizes the molecule whereas ABMO destabilizes thé molecules. Head on overlap or ming of atomic ofp) generates o molecular orbital whereas side wise or lateral overlap of atomic orbital generat molecular orbital o«BM0 ——> o ABMO ——>(" a° ™BMO ——>* TM ABMO a> _ Shape of Molecular Orbitals:- 4. Mixing of 13 or 2s atomic orbitals:| The o bonding molecular orbital and o* antibonding molecular orbital_are_shown_in_the molecular orbital diagram below. In an MO diagram, the energies are represented as horizontal lines; the bottom line is the lowest energy level, the top line the highest energy level. We see that any electrons in the bonding orbital will most likely be found between the nuclei. This increased electron density between the nuclei is what binds the atoms together. Because there is a node between the nuclel in the antibonding molecular orbital, any electrons that are in that orbital are more likely to be found anywhere except between the nuclel, so the nuclel are more exposed to one another and will be forced apart by electrostatic repulsion. Thus, electrons that occupy this, orbital detract from, rather than aid, the formation ofa bond between the atoms. ‘tal2. Mixing of 2p atomic orbitals: Two p atomic orbitals can overlap either end-on or side-to-side. Let's first look at end-on overlap. End-on overlap forms ao bond. If the overlapping lobes of the p orbitals are in-phase (a blue lobe of one p orbital overlaps a blue lobe of the other p orbital), a o bonding molecular orbital is formed. The electron density of the o bonding molecular orbital is concentrated between the nuclei, which causes the back lobes (the nonoverlapping lobes) of the molecular orbital to be quite small. The o bonding molecular orbital has two nodes—a nodal plane passing through each of the nucleiIf the overlapping lobes of the p orbitals are out-of-phase (a blue lobe of one p orbital overlaps a green lobe of the other p orbital), a o* antibonding molecular orbital is formed. The antibonding molecular orbital has three nodes. (Notice that after each node, the phase of the molecular orbital changes.) Energy Unlike the @ bond formed as a result of end-on overlap, side-to-side overlap of two p atomic orbitals forms a pi m bond (Figure 1.6). Side-to-side overlap of two inphase p atomic orbitals forms am bonding molecular orbital, whereas side-to-side overlap of two out-of-phase p orbitals forms a m* antibonding molecular orbital. The m bonding molecular orbital has one node—a nodal plane that passes through both nuclei. The n* antibonding molecular orbital has two nodal planes. Notice that bonds are cylindrically symmetrical but 1 bonds are not.‘The extent of overlap is greater when p orbitals overlap end-on than when they overlap side-to-side. This means that a o bond formed by the end-on overlap of p orbitals is stronger than ar bond formed by the side-to-side overlap of p orbitals. It also means that a « bonding molecular ortital is more stable than a r bonding molecular orbital because the stronger the bond, the more stable it is. Below Figure shows a molecular orbital diagram of two identical atoms using their three degenerate atomic orbitals to form three bonds—one o bond and two m Ss 2 - > aa otiut \@- Veg / aetomic ‘orb bonding molecular orbitalp Orbitals can overlap end-on to form o bonding and o* antibonding molecular orbitals, or can overlap side-to-side to form m antibonding molecular orbitals. The relative energies of the imoleuar vite — Ly © © © ® 8 Now let’s look at the molecular orbital diagram for side-to-side overlap of a p orbital of carbon with ap orbital of oxygen—the orbitals are the same, but they belong to different atoms (below figure). When the two p atomic orbitals combine to form molecular orbitals, they do so unsymmetrical. The atomic orbital of the more electronegative atom contributes more to the bonding molecular orbital, and the atomic orbital of the less electronegative atom contributes more to the antibonding molecular orbital. This means that if we were to put electrons in the bonding MO, they would be more apt to be around the oxygen atom than around the carbon atom. Thus, both the Lewis theory and molecular orbital theory tell us that the electrons shared by carbon and oxygen ere not shared equally—the oxygen atom of a carbon-oxygen bond has a partial negative charge and the carbon atom has a partial positive charge.Organic chemists find that the information obtained from MO theory, where valence electrons occupy bonding and antibonding molecular orbitals, does not always yield the needed information about the bonds in a molecule. The valence-shell electron-pair repulsion (VSEPR) model combines the Lewis concept of shared electron pairs and lone-pair electrons with the concept of atomic orbitals and adds a third principle: the minimization of electron repulsion. In this model, atoms share electrons by overlapping their atomic orbitals, and because electron pairs repel each other, the bonding electrons and lone-pair electrons around an atom are positioned as far apart as possible. = anthonding molecular bey # ot oxygen bonding molecular> Filling of Molecular orbital Sequenes}When total electrons remorethan 4 - + asso" 15,025 2seo2o2\m29x= N2p¥'N" 2px= n’ 2py.o" pz | VO ere ase total electrons aré less than or equal to 14 (pina 2s, n2px = M2py, 02pz, n° 2px=m py, O° 2pz ° KE cate o* ~o ‘nom’ * umn Aron te § Electrons are distributed amon are according to aufbau’s, Hund’s and Pauli’s principle i.e. * Each molecular orbital can accommodate a maximum of two electrons of opposite spins. * Electrons occupy lowest energy molecular orbital. Higher energy orbitals will not be filled as long as low energy orbitals are available.Bond Order: - Bond order is a number which indicates the no. of bonds a molecule possesses / and the stability of the molecule in comparison to another. An integral value implies that so {many bonds exist in the molecule. Anything fractional indicates that the bond is intermediat; (aet| aoe) ME a Where, n, and n, are electrons in BMO and ABMO respectively. Bond Order a Bond dissociation energy a Stability ~~ 1/Bond Length = Iftwo species have same bond order then that species will be more stable in which more number of V7 electrons are present in BMO. o= , Gad a? K 60= 0 tS esBO = 1 (single bond), BO = 2 (double bond), BO = 3 (Triple Bond), BO =.0 (Molecules doesn’t exists) (Note:- Before discussing above mentioned points it is necessary to understand the term paramagnetism and diamagnetism. Poramagnetic substances are those substances which attract towards magnetic field if they are placed in a magnetic field whereas diamagnetic substances are repelled by magnetic field. The magnetic behavior of a substance is measured by the term magnetic moment{(y) w = n(n +2) B.M. Where, n = number of unpaired electrons present in the substance B.M = Bohr magneton (a unit of magnetic moment) It means that fa unpaired electrons are present in a substance its magnetic moment () will be non-zero Gnd it will be a paramagnetic substance. Similarly, it substance doesn’t contain unpaired electrons _its-magnetic moment will be zero and substance will be diamagnetic.)Let us take some examples to clear above points: (a). Hz 2 Totalelectrons — Bond order = % (2-0) i.e. two H atoms are joined together by single bond, “= "— oO - a I os) Ca ‘ ac Ss macs Sea) Se pede? D> ae Me" ! H(AO) MOs) H (AQ) ———= Since, unpaired electron is absent in H, thysitis colorless nd diamagnetic: So,n=0 => ws /nin+2)=Q8m6. Molecular Orbital Theory ce lea > . => + <> i) ie How do atoms form covalent bonds in order to form molecules? The Lewis model, which describes how atoms attain a complete octet by sharing electrons, tells us only part of the story. A drawback of the ‘model is that it treats electrons like particles and does not take into account their wavelike properties. This theory was proposed by Robert Mullikan and he explained the paramagnetic behavior of 0, which is diamagnetic according to valance bond theory. ‘Molecular orbital (MO) theory combines the tendency of atoms to fill their octets by sharing electrons (the Lewis model) with their wavelike properties—assigning electrons to a volume of space called an orbital. According to MO theory, covalent bonds result from the combination of atomic orbitals to form molecular orbitals— orbitals that belong to the whole molecule rather than to a single atom. Like an atomic orbital that describes the volume of space around the nucleus of an atom where an electron is likely to be found, a molecular orbital describes the volume of space around a molecule where an electron is likely to be found. Like atomic orbitals, molecular orbitals have specific sizes, shapes, and energies.Based on this, it can be concluded that electrons behaving as waves can interact with each other and the process is called interference. As in waves, two types of interferences are possible: (1) constructive and (2) Destructive. In molecules the atomic orbitals of all the atoms are assumed to interfere with each other in the form of waves and depending on the nature of interferences, two molecular orbitals result. The one which results from constructive interference is called bonding molecular orbital (BMO) and the one which results from destructive interference is called anti-bonding molecular orbital (ABMO). Obviously anti bonding MO is of higher energy than Bonding MO. In Molecular Orbital Theory (MOT) the atoms in a molecule are supposed to loose their individual control over the electrons. The nuclei of the bonded atoms are considered to be present at equilibrium inter-nuclear positions. The orbitals where the probability of finding the electrons is maximum are multicentred orbitals called molecular orbitals extending over two or more nuclei. ‘As mentioned above, when a pair of atomic orbitals combine they give rise to a pair of molecular orbitals, the bonding and the anti-bonding. The number of molecular orbitals produced must always be equal to the number of atomic orbitals involved. Electron density is increased for the bonding MO’s in the inter-nuclear region but decreased for the anti-bonding MO’s, SI 1g of the nuclei by increased electron density in bonding MO’s reduces inter nuclei repulsion and thus stabilizes the molecule whereas lower electron density even as compared to the individual atom in anti-bonding MO’s increases the repulsion and destabilizes the system\ f° é 4 oN B BM.O (A.B.M.0) In ABMO there is one nodal plane bisecting perpendicularly the internuclear axis. BMO stabilizes the molecule whereas ABMO destabilizes the molecules. Head on overlap or mixing of atomic orbital generates o molecular orbital whereas side wise or lateral overlap of atomic orbital generates m molecular orbital. 0 8MO ——* o 0 ABMO ——> 0° ™BMO ——> Tt mABMO ——>> Shape of Molecular Orbitals:- 1. Mixing of 1 or 2s atomic orbitals: The 0 bonding molecular orbital and o* antibonding molecular orbital are shown in the molecular orbital diagram below. In an MO diagram, the energies are represented as horizontal lines; the bottom line is the lowest energy level, the top line the highest energy level. We see that any electrons in the bonding orbital will most likely be found between the nuclei. This increased electron density between the nuclei is what binds the atoms together. Because there is a node between the nuclel in the antibonding molecular orbital, any electrons that are in that orbital are more likely to be found anywhere except between the nuclel, so the nuclel are more exposed to one another and will be forced apart by electrostatic repulsion. Thus, electrons that occupy this, orbital detract from, rather than aid, the formation of a bond between the atoms. a Ze H+-@2. Mixing of 2p atomic orbitals: Two p atomic orbitals can overlap either end-on or side-to-side. Let's first look at end-on overlap. End-on overlap forms ao bond. If the overlapping lobes of the p orbitals are in-phase (a blue lobe of one p orbital overlaps a blue lobe of the other p orbital), a o bonding molecular orbital is formed. The electron density of the o bonding molecular orbital is concentrated between the nuclei, which causes the back lobes (the nonoverlapping lobes) of the molecular orbital to be quite small. The o bonding molecular orbital has two nodes—a nodal plane passing through each of the nucleiIf the overlapping lobes of the p orbitals are out-of-phase (a blue lobe of one p orbital overlaps a green lobe of the other p orbital), a o* antibonding molecular orbital is formed. The antibonding molecular orbital has three nodes. (Notice that after each node, the phase of the molecular orbital changes.) @s'eD> ‘9° antibonding nol orbial ne oo Post Sn J Energy bonding molcolr eit Unlike the @ bond formed as a result of end-on overlap, side-to-side overlap of two p atomic orbitals forms a pi m bond (Figure 1.6). Side-to-side overlap of two inphase p atomic orbitals forms am bonding molecular orbital, whereas side-to-side overlap of two out-of-phase p orbitals forms a m* antibonding molecular orbital. The m bonding molecular orbital has one node—a nodal plane that passes through both nuclei. The n* antibonding molecular orbital has two nodal planes. Notice that bonds are cylindrically symmetrical but 1 bonds are not.‘The extent of overlap is greater when p orbitals overlap end-on than when they overlap side-to-side. This means that a o bond formed by the end-on overlap of p orbitals is stronger than ar bond formed by the side-to-side overlap of p orbitals. It also means that a « bonding molecular ortital is more stable than a r bonding molecular orbital because the stronger the bond, the more stable it is. Below Figure shows a molecular orbital diagram of two identical atoms using their three degenerate atomic orbitals to form three bonds—one o bond and two m bonds. (sea) 36 1 antibonding molecular orbital bonding molecular orbitalp Orbitals can overlap end-on to form o bonding and o* antibonding molecular orbitals, or can overlap side-to-side to form m bonding and n* antibonding molecular orbitals. The relative energies of the molecular orbitals areo Filling of Molecular orbital Sequence (A):-When total electrons are more than 14 01s, 0° 1s, 02s, 0° 2s, o2p2, n2px=n2py, n’ 2ox=n' Qpy, 0" 2pz ‘Sequence (8):- When total electrons are less than or equal to 14 Ols, os, 02s, 0" 2s, n2px = m2py, o2pz, m 2px= 1 2py, o” 2pz es s~ 2@( @ \o Fre ~ a rr) 3 g 1000" e otal 8 Electrons are distributed among the molecular orbitals according to aufbau’s, Hund’s and Pauli’s principle i.e. * Each molecular orbital can accommodate a maximum of two electrons of opposite spins. * Electrons occupy lowest energy molecular orbital. Higher energy orbitals will not be filled as long as low energy orbitals are available.> Bond Order: - Bond order is a number which indicates the no. of bonds a molecule possesses and the stability of the molecule in comparison to another. An integral value implies that so many bonds exist in the molecule. Anything fractional indicates that the bond is intermediate. B.O=1/(Mp-Na) Where, n, and n, are electrons in BMO and ABMO respectively. Bond Order a Bond dissociation energy @ Stability a 1/Bond Length Iftwo species have same bond order then that species will be more stable in which more number of electrons are present in BM(BO = 1 (single bond), BO = 2 (double bond), BO = 3 (Triple Bond), BO = 0 (Molecules doesn’t exists) (Note:- Before discussing above mentioned points it is necessary to understand the term paramagnetism and diamagnetism. Paramagnetic substances are those substances which attract towards magnetic field if they are placed in a magnetic field whereas diamagnetic substances are repelled by magnetic field. The magnetic behavior of a substance is measured by the term magnetic moment (1) uo Jn(n+2) BM Where, n = number of unpaired electrons present in the substance B.M = Bohr magneton (a unit of magnetic moment) It means that if a unpaired electrons are present in a substance its magnetic moment () will be non-zero and it will be a paramagnetic substance. Similarly, it substance doesn’t contain unpaired electrons its magnetic moment will be zero and substance will be diamagnetic.)Let us take some examples to clear above points:- (a). Hee Total electrons =2 ie.o1s,o"1s° Bond order = % (2-0) =1 i.e. two H atoms are joined together by single bond. e| —— = Is 1s Os H(AQ) H, (MOs) H (AQ) Since, unpaired electron is absent in H, thus it is colorless and diamagnetic. So,n u= /n(n+2)=08M> fen — ye) ° — ss BS eon a a rn A ae ceemaiad ore —