Module ATOMIC & MOLECULAR STRUCTURE Weightage : 16 Marks Atomic otbitals (s, p, d, f) orbital shapes, Electronic Configuration, Molecular orbital theory .(MOT),.. bonding. and anti-bonding orbitals, Molecular orbital. diagrams of Homonuclear and Heteronuclear diatomic molecules-Be,, Oz, CO, NO their bond ‘order and magnetic properties 1.1 Introduction 1.2 Concept of Shells and sub-shells 1.3 Quantum Numbers 1.4 Graded Questions Gdlo Khrd 9Enq’ mx pt dx Vg" s @o wi 6/ 3 4/ 0 74 28 “ef dsteRnkdo-2I Vidyalankar : F.E. - Chemistry I 11 INTRODUCTION An atom is defined as the smallest particle of an element showing all the characteristics of the element. ‘A molecule is defined as the smallest particle of a compound showing all the characteristics of the compound ‘A compound is the substance formed by combination of two or more atoms. When molecule is formed by combination of two atoms of same or different kind, it is known a diatomic molecule. e.g. Oz, He, HCI, No, CO, NO, Cle, etc. When a molecule is formed by union of three atoms of same or different kind, it is known as triatomic molecule, e.g. H,0, O53, HS, CO2, NOz, ete. 14 Qt Ans.: 1.2 1.24 Qt Ans.: Fundamental Particles of Atom What are the fundamental particles of atom? Atom of an_element consists of three types of particles which are known fundamental or subatomic particles — (1) Electron, (2) Proton, (3) Neutron. Electron was discovered in 1896 by J. J. Thomson. Proton was discovered by Goldstein in 1911 and Neutron was discovered by Chadwick in 1932, Protons and neutrons are present at the centre of atom in a small shape called nuclear Protons are positively charged, therefore the nucleus of atom is positively charged. Electrons are negatively charged particles and revolve around the small nucleus. Protons and neutrons are also called as nuclear particles or nucleons and electrons are called as extra nuclear particles. According to Dalton's theory, atom is indivisible and consists of positively charged protons, negatively charged electrons and chargeless neutrons. Different atomic models were proposed to explain the distribution of these sub- atomic particles. Some of these models are Thomson's model, Rutherford's models, Bohr's model, etc. Bohr’s model suggested the presence of shells and sub-shells in the atomic model. CONCEPT OF SHELLS AND SUB-SHELLS Shells Explain the concept of shells and sub-shells with reference to the atom. According to Bohr’s atomic model, electrons revolve around the nucleus in stationary energy levels called orbits. These orbits are also known as principal energy levels or shells. These energy levels are represented by Principal Quantum Number, n, which assumes only integral values 1, 2, 3 ... , so on. The shells are also represented by letters K, L, M, N_ so on. The energy of the shell goes on increasing as the distance of the shell increase from the nucleus. For n= 1, electron is present in the first shell K. For n = 2, itis present in L shell and 80 on. The energies of electrons of the shells increase from K shell onwards. The maximum number of electrons in any shell is given by ‘2n* where n = 1,2,3, .. $0 on. Thus K shell contains 2 electrons, L shell contains 8 electrons. M shell contains 18 electrons, N shell has 32 electrons, and so on.Module 1 : Atomic & Molecular Structure 3 1.2.2 Q2 Ans.: Sub-shells Each shell is divided into sub-shells. They are designated as s, p, d, f. Here s stands for sharp, p stands for principal, d stands for diffused and f stands for fundamental. Each sub-shell in a shell is assigned on Azimuthal Quantum Number, /, For a given value of n, /, can have values ranging from 0 to (n - 1) For 's’ sub-shell, /=0; For ‘p’sub-shell, / = 1; For ‘d’ sub-shell, /!>!2 For‘ sub-shell, //>3 ! * Total number of sub-shells in a main shell (with a given value of n), is equal to‘n’ It means when n = 1, then there will be only one sub-shell ‘s’ and / = 0. For n= 2, the number of sub-shells will be two's’ and ‘p’, £ = 0, 1 When n= 1, then shell K will contain only one sub-shell i.e. 1s. L shell (n = 2) contains two sub-shells, 2s, 2p. M shell (n = 3) contains three sub-shells, 3s, 3p, 3d. N shell (n = 4) contains four sub-shells, 4s, 4p, 4d, 4f Following Table shows the number of sub-shells for each shell Principal shell |__Number of sub-shells Designation of sub-shells, K 1 is L 2 2s, 2p M 3 3s, 3p, 3d N 4 4s, 4p, 4d, 4F ° 5 5s, 5p, 50, 5f, Number of sub-shells for each shell The maximum number of electrons in a given sub-shell is given by 2(2/ + 1). Thus, s = sub shell (/ = 0) contains 2 electrons p= sub shell (/ = 1) contains 6 electrons d= sub shell (¢ = 2) contains 10 electrons f = sub shell (/ = 3) contains 14 electrons. 2 Graphically, sub-shells can be represented as} 3 aaa shown in figure, weaesang 2 nea >From graph, energy of 3d sub-shell is higher 20 than that of 4s sub-shell. It means that the | na energy of sub-shell is higher than that of a 7 shell for the same value of n. Gamegear Orbitals What are the orbitals? The density of electron cloud is not uniform everywhere around the nucleus. There is a particular region in which electron cloud is more dense. In this region the probability of finding an electron is maximum. Such a region is referred to as an orbital. Thus, the three dimensional region in the space around the nucleus in which the probability of finding electron is maximum is called pscjubaiin an orbital, there may be regions of high probability and regions of low probability. In each orbital, the electron has a definite energy. The energy of an orbital is lower if it is concentrated near the nucleus. It is to be noted that an orbital is not the same as an orbit. The two differ in several respects. Table shows the differences between an orbit and an orbital4| — Vidyalankar : F.E. - Chemistry I @.3 Give the differences between the Orbit and Orbital Ans.: Orbit Orbital T, |itis well defined circular path around itis a three dimensional space Ithe nucleus in which electrons Jaround the nucleus in which the Irevolve according to Bohr’s model of probability of finding an electron is lan atom. maximum. This is in accordance with quantum mechanical model of atom. 2. [An orbit can accommodate an An orbital can accommodate lelectrons where nrepresents the [maximum of 2 electrons only. lnumber of orbit. S. |The revolution of electron in an orbit is |Concept of orbital is in accordance lagainst the Heisenberg’s uncertainly —_|with the uncertainty principle. principle. 4, [Orbits are circular. [The probability distribution of charge cloud in different orbitals is different. This gives them different shapes. 5, [Orbits are non-directional. Except s orbital all other orbitals are directional in nature. 1.3. QUANTUM NUMBERS Q.1 What are Quantum Numbers? Explain them in detail. Ans.: The numbers which identity the state of an electron, specify the energy associated with it, and its location around the nucleus are called quantum numbers. These numbers are used to designate and distinguish electrons in atomic orbitals. There are four quantum numbers: Principal quantum number (n), Azimuthal quantum number (), Magnetic quantum number (m), and Spin quantum number (s). (a) Principal quantum number (n) This number represents the main shell to which It defines the distance of electron from the nucleus and its energy level. It n= 1,2,3,4,5,6,7 . also represented by letters K, L, M, N, 1, is the nearest to the nucleus and has least energy. The energy of the the electron belongs. has the values, first energy level n = main shell increases as on. the value of ‘n’ increases. Each main shell contains a maximum of 2n* electrons. Thus, K shell (n = 1) contains maximum of two electrons. L shell (n = contains maximum of 8 electrons. (n =3) contains maximum of 18 electrons, and so Principal quantum number provides two They are The os Q )) a e ° Fig. : The Principal shells and the quatum numbers (n) 2) M shell important information's, i.e., the principal (main) shell to which an electron belongs, and the energy of the principal shell.Module 1: Atomic & Molecular Structure [5 (b) Azimuthal Quantum Number (¢) This is also called secondary, subsidiary, orbital or Angular momentum quantum number. It represents the sub-shell to which the electron belongs. It defines the shape of the orbital occupied by the electron and the angular momentum of the electron. Its values depend upon the value of principal quantum number, n. It can have only positive values between 0 and (n - 1). where 'n' is the principal quantum number. Thus, the permissible values of '/” are 0,1,2,3 ... (n-1). This quantum number provides the following informations: (i) The sub-shell in which the electron is present. A principal shell in an atom is composed of sub-shells. These sub-shells are represented by s, p, d, f. These letters are derived from the terms sharp, principal, diffused, and fundamental. These terms are used in spectroscopy to describe the nature of spectral lines present in the emission spectrum of an atom. When £= 0, itis‘s"'sub-Shell. When / = 1, it is ‘p’ sub-shell. When ¢ = 2, it is ‘d’ sub-shell, When ¢= 3, itis ‘f’ sub-shell. (ii) The number of sub-shells present in a principal shell. The values of ‘/ depend upon the value of ‘n’. The azimuthal quantum number signifies the number of sub-shells which a principal shell can possess. (Table) Table : Principal shell and sub-shell Principal | Value of | Permissible | possible | Number of shell ‘n value of ‘¢" | sub-shell | SUb-shell in shell K 7 0 3 7 L 2 04 SP 2 M 3 0.1.2 Spd 3 N 4 01423 [spat 4 It can be seen from the Table that the total number of sub-shells present in a principal shell is equal to the principal quantum number ‘n’ of the shell. The sub-shell of a particular shell are specified by putting the value of ‘n’ before the symbol of sub-shell. Thus, n= 3, and f = 0, corresponds to 3s sub-shell. n= 3, and f = 1, corresponds to 3p sub-shell. n=4, and ¢ = 2, corresponds to 4d sub-shell. (iii) The shape of sub-shell : The azimuthal quantum number ‘/’ is responsible for particular shape of particular shell because it defines the spatial distribution of the electron cloud around the nucleus. (iv) The angular momentum of the electron : The quantum number ‘/” is used to calculate the angular momentum of an electron in a particular sub-shell. The orbital angular momentum ‘L’ of an electron in a sub-shell with azimuthal quantum number ‘/’ is given by rere onoe LaPeer 2aVidyalankar : F.E. - Chemistry I where, h = Planck's constant. Each sub-shell contains a maximum of 2 (2£ + 1) electrons. Thus, ‘s’ orbital contains a maximum of 2 electrons, ‘p-orbital contains 6 electrons, ‘d’ orbital contains 10 electrons and ‘f orbital contains maximum 14 electrons. () Magnetic Quantum Number (m) This quantum number is used to explain Zeeman effect. The values of ‘m’ are govemed by values of ‘/’ . It can have any integral value between -( and + £ through zero. Thus, ME Cece 2A, O, + Wt Qerrear +E Thus, for a given value of ‘/’, 'm' will have (2¢ + 1) values. A sub-shell in an atom’ is composed of several orbitals. The magnetic quantum number ‘m’ tells us about to which orbital an electron belongs. It also tells us the number of orbitals which corresponds to a particular shell. Thus, (a) For‘s'- sub-shell, ¢=0 -.m=0. This means that the 's’ sub-shell contains only one orbital, i.e., s-orbital. (b) For 'p'- sub-shell, ¢ = m= 410-1, 'p'= sub-shell contains three orbitals, py, py and pz. In the absence of magnetic field, all the three p-orbitals have equal energies, i.e., they are degenerate. (©) For ‘d= sub-shell, (/=2 sm = +2, +1, 0,-1, -2. ‘d' - sub sub-shell contains five orbitals, dyy, dye, Gees does de In absence of magnetic field, these are degenerate. (d) for sub-shell, #=3 -m=+#3,+241,0-1,-2,-3 ‘f — sub-shell contains seven degenerate orbitals. (d) Spin Quantum Number (s) : This quantum number accounts for the spin of electron. An electron can spin clockwise or anticlockwise, in two opposite directions. There are two possible values of ‘s’ that are equal and opposite. The probability of rotation in one direction is only 1/2. Therefore, the spin quantum number can have only two values: + 1/2 and - 1/2. For clockwise spin value is + 1/2 and for anticlockwise. spin. value is ~ 1/2. Two electrons with the same sign of the spin quantum number are said to have parallel_spins while those having opposite signs of the spin quantum number are said to have opposite spins or antiparallel spins. Since spinning charge is associated with a magnetic field, an electron must have a magnetic moment associated with it Magnetic Clockwise and anticlockwise spin of electrons about their own axes produced opposite magnetic fields.Module 1: Atomic & Molecular Structure 7 The values of ' /’ and the corresponding values of'm' are shown in Table. The values of ‘ /’ and the corresponding values of ‘m’ lVatud sub-| Value of m— / | Total number of value] No. of | Maximum of (| shell to+ f of m orbital | hUMBErS of electrons 0] s 0 One value ofm, soone | 1 2 orbital ie., s orbital 1 Pp -1,0, +1 Three values of m, so 3 6 three orbitals ps. py. P; 2| 4 2,1, 0, +1, +2 | Five values of m, so 5 10 five orbitals at ~2 1, 0, +1, | Seven values of m, so | 7 4 42.43 seven orbitals The values of quantum numbers ‘/’ and ‘m' forn'=1 to 4 principal shell and give in Table. The values of quantum numbers */ and ‘m’ for n = 1 to 4 principal shell Principal] Value of Value of 7 Value of m | Total No. of shell n Oton-1 =f tof electrons K 1 ©) mm 2 (s) m. L 2 (p) m 8 m m TOs) m. EAB m m m M. 3 m 18 m T=20) m m m m. ™m m m 7=2@ ™m m m N 4 m 32 m 30) m m m m=0 m=+1 m=+2 m=+38| _ Vidyalankar : F.E. - Chemistry | 1.3.1 Different Shapes Orbitals @.2 Give the different shapes of the following orbitals : (i) s-orbitals, (ii) p-orbitals, (iii) d-orbitals. Ans.: () s-orbital For s-orbital, ¢ = 0 and for / = 0, m = 0. This shows that s-orbitals have only one orientation. They are spherically symmetrical about the nucleus. For each value of principal quantum number ‘n’ , there is only one orientation for ¢ = 0 (s-orbital), i.e.-!there is only one s-orbital for given ‘n’. There is only one symmetrical orbital for each value of ‘n’, whose radius depends upon the value of ‘n’. The size of an orbital depends upon the value of ‘n’. As the value of ‘n’ increases, the size of the s-orbital increases. 2s orbital is bigger than 1s , 3 sis bigger than 2s and so on. In between 1 s and 2 s, there is a region where probability of finding the electron is zero, It is called as/‘node'/Figure shows the shapes of 1s, 2s and 3s orbitals. Roce 7 4 : odes as orbitat 2s orbital 3s orbital Shapes of 1s, 25 and 3s orbitals (ii) p- orbitals For p-orbital, ¢ = 1, For ¢= 1, m= + 1, 0, - 1. Thus, p-orbitals have three orientations, p-orbital is dum-bull shaped. Each orbital consists of two lobes The two lobes are separated by a plane having zero electron density. Such a plane is called ‘nodal plane’. Figure shows the ‘nodal plane’ and three p- orbitals which are designated as px, py and pz. Nodat peor py-rptal protiat Shapes of p-orbitals Three p-orbitals p,, py and pe, are perpendicular to each other and oriented along x, y and z axes respectively in space. They are equivalent in energy in the absence of magnetic field. (ii) d-orbitals For d-orbitals, / = 1. For (= 2,m=+2,+1,0, 2. Thus, d-orbitals have five orientations. They are designated as dy, dyzs Giz J» je » de. They all1.3.2 a3 Ans.: 1.3.3 Q4 Ans.: Module 1 : Atomic & Molecular Structure | 9 are equivalent in energy in the absence of magnetic field. The first three have double dumb-bell shape in xy, yz and xz plane, respectively. The d.. ,. is also dumb-bell shaped and lies along the x and y axes. The d.. is dumb-bell shaped with a dough-nut shaped ring of high electron density around the nucleus in xy plane. Shapes of d-orbitals are shown in Fig. Shapes of orbitals. Electronic Configuration What is meant by Electronic Configuration of an element? The electronic configuration is the standard method used to explain the electronic structure of an atom. The electrons occupy the orbitals. The distribution of electrons in various shells, sub-shells and orbitals of an atom is known as its electronic configuration. Many of the physical and chemical properties of elements can be determined. by using the electronic configurations, specially the valence electronic configurations, i.e., outermost electronic configurations. The filling up of electrons in orbitals has to follow three rules. namely, Aufbau Principle, Paul's Exclusion Principle, and Hand's Rule of Maximum multiplicity. Electronic Configuration Explain the following rules which have to be followed for filling up of electrons in different orbitals: (i) Aufbau Principle, (ii) Pauli's Exclusion Principle, Hund's Rule of Maximum Multiplicity. The Rules for Filling Electrons in Orbitals : The distribution of electrons in various shells, sub-shells and orbitals of an atom is known as its electronic configuration. Generally, electronic configuration of an atom is written as n/* . where n= shell number, / = sub-shell and x = number of electrons, e.g. 3p” means _n = 3, i.e. ,shell number; / = 1, i.¢., sub-shell and 2 is the number of electrons. Electronic configuration is mainly explained by following rules : (1) Aufbau Principle (2) Pauli's Exclusion Principle (3) Hund's Rule of Maximum Multiplicity.10] Vidyalankar : F.E. - Chemistry I (1) Aufbau Principle : Aufbau is a German term which means ‘Building up’. The principle explains the order in which various orbitals are filled with electrons. According to Aufbau Principle, "In the ground state of the atoms, the orbitals are filled with electrons in order of the increasing energies." Electrons enter the orbitals according to following (n +/*rules: (i) Orbitals are filled in order of increasing value of (n +/). ¢.9., consider 3d and 4s ofbitals. For 3d,n=3 and / =2 (N+ )=342=5 For 4s,n=4 and / =0 e(N4)=4412=5 As the value of (n + /) for 4s orbital is less than that of 3d orbital, 4s orbital is filled before 3d orbital. (ii)-1t two orbitals have same value of (n + /), then the orbital with lower value of n will be filled first, e.g., Consider 3d and 4p orbitals. For 34,n=3 and ¢ =2 (n+) =342=5 For 4p,n=4 and f = cnt Q=44 =4 As the value of n = 3, for 3d orbital, it will be filled up before 4p orbital. The order of energy of different orbitals in an atom can be represented by the (n+) * Fig. : Aufbau principal The order of energy of different orbitals in an atom is given as : 1s < 28 < 2p < 38 < 3p < ds < 3d < dp < 5s < dd < Sp < 6s < Af < Sd < 6p < 7s < Sf < 6d < 7p < 8s and so on.(2) (3) Module 1 : Atomic & Molecular Structure | 11 Pauli's Exclusion Principle : This principle limits the number of electrons that can occupy any orbital of an atom. It states that "Two electrons in an atom cannot have the same set of all four quantum numbers." In other words, "Only two electrons may exist in the same orbital with three quantum numbers same, i.e., the fourth quantum number different and these electrons must have opposite spins." [4] Consider He atom. Its atomic number is 2. Electronic configuration is 1s” It has two electrons in 1s orbital. The four quantum numbers for two electrons in 1s orbital are given in Table. Quantum numbers Electron Quantum number number 7 7 ™ 3 T™ electron 1 0 0 +172 2” electron 1 0 0 1/2 Thus, in an atom, any two electrons may have the same value for any of three quantum numbers. The fourth quantum number must be different. This means that an orbital can accommodate maximum of two electrons, with opposite spins. According to this principle the values of quantum numbers are given in the Table Principal | Azimuthal | Magnetic Spin _] Total number of quantum | quantum quantum, quantum electrons number | _number number number n 7 m s on 1 0 22 2(8) > 2 2 0 V2 2(s) 8 1 212 6 (p) 3 0 2 2s) \ il 12 6 (p) $18 2 21/2 10(d) 4 0 +12 2s) 1 £12 6) Lo 2 +12 10(d) 3 212 14(F) Hund’s Rule of Maximum Multiplicity : It states that “When several orbitals of equal energy (degenerate orbitals) are available, the electrons first fill all the orbitals singly before pairing in any of these orbitals. ration of four electrons occupying p-orbitals is #4) and12] Vidyalankar : F.E. - Chemistry I 1.3.4 Qs Ans.: a6 Ans.: Completely filled or half-filed orbitals give extra, stability. This means that configuration p° and p® are more stable than p', p*, p' and p®. Cr with atomic number 24 and Cu with atomic number 29, behave anomalously. Expected electronic configuration of Cros is 18%, 28°, 2p°, 3s”, 3p°, 4s°, 3d°, The 3d orbital is not half-filled. Hence, itis less stable. One 4s electron shifts to empty 3 orbital to make 4s and 4d orbitals half-filled, Thus Cr acquires stability as its electronic configuration becomes 18°, 2s", 2p°, 3s°, 3p®, 4s', 8d° . In this configuration, both 4s and 3d orbitals are half-filled which gives extra stability to Cr. Expected electronic configuration of Cuzs is 1s°, 28°, 2p°, 38°, 3p, 4s°, 3d° . The 3d orbital is neither half-filled nor completely filled, Hence, it is less stable, One 4s electron shifts to one half- filled 34 orbital to make 4s halt-fled and 3d completely filled, Thus, Cu acquires stability as its electronic configuration becomes 1s°, 2s°, 2p", 38°, 3p*, 4s', 3d’? . In this configuration, Sd_ombital is completely filled and 4s otbital is haif-filled which gives extra stability to Cu Molecular Orbital Theory (MOT) What is Molecular Orbital Theory? The molecular orbital theory was put forward by F. Hand and R. S. Mulliken in 1932 and it was later developed by 1. E. Lenard Jones and Charles Coulson. According to MOT, the atomic orbitals combine to form new orbitals called molecular orbitals. The combining atomic orbitals must be of comparable energies and proper symmetry, An electron in an atomic orbital is influenced by ‘one nucleus, whereas in a molecular orbital, it is influenced by two or more nuclei depending upon the number of atoms in a molecule. Thus, an atomic orbital is monocentric while a molecular orbital is polycentric. According to Valence Bond Theory (VBT), atomic orbitals retain their identity ina molecule. According to MOT, atomic orbitals donot retain their identity. Atomic orbitals combine to form new set of orbitals called molecular orbitals in a molecule. The number of molecular orbitals formed is equal to the number of combining atomic orbitals. Just as atomic orbitals are designated as s, p, d, f orbitals and are determined by quantum numbers, molecular orbitals are also determined by quantum numbers and are designated as o, 7, o orbitals. Molecular orbitals obey the following rides as do atomic orbitals. Electron filling is in accordance with Aufbau Principle, obeying Pauli's Exclusion Principle and Hund's Rule of Maximum Multiplicity. The molecular orbitals are formed by Linear Combination of Atomic Orbitals (LCAO Method). Explain LCAO method with reference to MOT. OR Give diagrammatic representation of the Molecular Orbital Diagram Linear Combination of Atomic Orbitals (LCAO Method) : According to wave mechanics, the atomic orbitals can be expressed by wave functions, y's! which represent the amplitude of electron waves. The LCAO method is preferred because, it is difficult to solve the Schrodinger’s equation exactly, which would have given all the informations about these orbitals. It isModule 1 : Atomic & Molecular Structure | 13 1.3.5 az Ans.: assumed that the nature of molecular orbital can be obtained by combining the atomic orbitals of atoms which form the molecule. Since the electrons are most likely to be in the vicinity of the nuclear due to attraction, it is assumed that the molecular orbital should be nearly the same as the atomic orbital. By combining the atomic orbitals A and B, we get two molecular orbitals : a+ VB ve (i) Vat VB = (i) In the above equations (@) ya and yg are the wave functions of the atomic orbitals of atoms A and B respectively. (b) yp and a are the wave functions of bonding molecular orbital and anti- bonding, molecular orbital respectively. (c) We canwrite, e.g., (ii) as ye and ya without any change of meaning. Thus, when two atoms come closer to one another, two atom’s orbitals (one from each bonded atom) having comparable energy, same symmetry and possessing large overlaps, combine to form two molecular orbitals. One of them has lower energy and other has higher energy than the combining atomic orbitals. The molecular orbital with higher energy gives rise to a repulsive state and is called as anti-bonding molecular orbital, ys The molecular orbital with lower energy gives rise to an attractive state and is called as bonding molecular orbital, yp. This can be shown diagrammatically as Fig. The electrons placed in bonding molecular orbital tend to decrease the energy of the molecule and increase its stability. The electrons placed in anti-bonding molecular orbital try to increase the energy of the molecule and hence decrease its stability. Fig.: Molecular orbital Bonding and Anti-bonding Molecular Orbitals What are bonding and anti-bonding molecular orbitals? ‘A wave has crest and trough as shown in Figure. A property of a wave function y is its algebraic sign which may be + ve or ve and it is not to be confused with the sign of charged body. It depends upon the value of the coordinates. Squaring the wave function Fig.: Crest and trough gives electron density or the probability. of awave Atomic orbitals combine and form the same number of molecular orbitals. There are two ways of combining atomic orbitals, i.e., electron waves : (i) By addition: Figure represents the combination of two 1s orbitals by addition. The dots in the figure represent the two nuclei. The electron wave above the imaginary horizontal line is given a +ve sign and that below the14 Vidyalankar : F.E. - Chemistry I line is given a -ve sign. In case of combination of atomic orbitals by addition, both the electron waves are on the + ve side, i.e. the same side. Such wave functions are regarded as in the same phase. AN —_ ZN Fig. :Combination of two 1s AOs by addition When the atomic orbitals with the same sign combine, their wave functions are in the same phase. This kind of combination gives rise to bonding molecular orbitals (BMO). Figure shows the formation of BMOs by addition of two AOs. OO=@— Co Same phase OO=&) Fig : Formation of bonding MOs by addition of two AOs In this molecular orbital, the region between the two nuclei is the place where there is overlap of the individual orbitals and hence there is greater probability of electron density in this region as shown in figure. Fig : Bonding MO (electron density) for Hz molecule (ii) By subtraction : In this type of overtap, the two waves are in the opposite directions. The wave functions of different signs may be regarded as out of phase. Figure shows the combination of two 1s orbitals by subtraction : Combination of two 1° AOs by subtraction. When the atomic orbitals with the opposite sign combine, their wave function out of phase. This kind of combination gives rise to anti-bonding molecularModule 1 : Atomic & Molecular Structure Lis as Ans.: 1. 2. 3. 4. 5. orbitals (AMO). They are designated by an asterisk (*). Figure shows the formation of AMOs by subtraction of two AOs: O-O- : Formation of anti-bonding MOs by subtraction of two AOs Electron density in a bonding orbital tends to be region around the nuclei as shown greater in the @p Nod! lane in Fig. In an anti-bonding orbital, the electrons are in those region in space where they are not under the attraction of both the nuclei. This is shown in Fig The formation. and the characteristics of bonding and anti-bonding molecular orbitals are given in Table. inti-bonding MO (electron density) for Hp molecule) How are molecular orbitals formed by addition and subtraction? Table : Bonding and Anti-bonding MOs Bonding MO Anti-Bonding MO Formed by addition of electron waves Wo= Wat Ve Formed by subtraction of electron waves Wa= Wa~Ve The two overlapping electron waves are on the same side, i.e., the signs of the two wave functions are same. The two overlapping electron waves are on opposite sides, i.e., the signs of the two wave functions are different. The electron density between the two nuclei is maximum and results in less intemuclear repulsion The electron density between the two nuclei is nil and results in more intemuclear repulsion. Energy is lower and hence is more stable than the overlapping atomic orbitals. Energy is higher and hence is less stable than the overlapping atomic orbitals. Overlap integral is positive and creates bonding situation. Overlap integral is negative and does not create bonding situation. Conditions for the combination of Atomic Orbitals The combining atomic orbitals must have same or nearly same energy. For example. 1s orbital can combine with another 1s orbital, but not with 2s orbital, as the energy of 2s orbital is higher than that of 1s orbital The combining atomic orbitals must have same symmetry about the molecular axis. For example, 2p,, orbital of one atom combines with 2p, orbital of another atom, but not with 2p, or 2p, orbitals because of their different symmetries. The combining atomic orbitals must overlap to the maximum extent. Greater the extent of overlap, the greater will be the electron density between the nuclei of molecular orbital 1.16| _Vidyalankar : F.E. - Chemistry | Sigma (0) and pi (n) Molecular Orbitals The molecular orbitals of a diatomic molecule are designated as o (sigma), Api), 5 (delta), etc. The symmetry of molecular orbitals of a diatomic molecule is shown in Fig O:0-© 0:0 — 0 CLOCLTOOO SBEM Ye Dito (0) Anti-bonding Pray + Poy (2) Bonding Oe O gd © Pied '(F) Anti-bonding Fig. Symmetry of molecular orbitals When the atomic orbitals overlap along the line joining the two nuclei (head-on), they form a(sigma) molecular orbitals. These are cylindrically symmetrical along the inter- nuclear axis. Combination of 1s with 1s and 2s with 2s gives rise to o molecular orbitals. Figure shows bonding o; molecular orbital formed by the combination (addition) of 's' atomic orbital of one atom with 's' atomic orbital of the other atom. Figure shows anti- bonding o, molecular orbital formed by subtraction of two ‘s' atomic orbitals of two atoms. Similarly, Fig. (¢) and (d) shows bonding and anti-bonding ope and anti bonding ©, molecular orbitals formed by addition and subtraction of two p; atomic orbitals of two atoms respectively.Module 1 : Atomic & Molecular Structure _| 17 When atomic orbitals overlap laterally (side ways), they form o! (pi) molecular orbitals. These have the inter-nuclear axis lying in a nodal plane to form ol(pi) bonds. Figure (e) shows x bonding molecular orbital and Fig. (f) shows nanti-bonding molecular orbital In (delta) molecular orbitals, the internuclear axis lies in two mutually perpendicular planes. The dy and d,.__ orbitals form & (delta) molecular orbitals. @.9 Differentiate between o (sigma) and x (pi) molecular orbital: Ans.: Table shows the differences between o and x/molecular orbitals. MO MO T. |The lobes of the AOs are in line with |The lobes of AOs are perpendicular the intemuclear axis. to the intemuclear axis. 2. [Formed by head on collision of AOs Formed by lateral overlap of AOs [Fig. c] [Fig. (e)] 3. |The electron density along the inter- |The electron density along the inter- nuclear axis is not zero (y* = 0) nuclear axis is zero (y* = 0) @ [Bonding MOs are gerade (even) and [Bonding MOs are ungerade (uneven) anti-bonding MOs are ungerade and anti-bonding MOs are gerade (uneven), (even), 5. [Forms stronger bond Forms comparatively weaker bond 1.3.6 Molecular Orbitals in Diatomic Molecules The diatomic molecule consists of two atoms. For the formation of stable molecule, the atomic orbitals of two atoms must combine according to LCAO method. The combining atomic orbitals must have (i) approximately the same energy, (ii) matching symmetry, and (ii) positive overlap to form bonding molecular orbitals Table gives the atomic orbitals which can combine to form molecular orbitals. The energy levels of molecular orbitals in diatomic molecules are shown in Fig. In the molecules are shown in Fig. In the molecular orbital diagram, the 1s bonding, oi. orbital and the anti-bonding, 7, orbital, have the lowest energies. The 2s atomic orbitals form next higher energy orbitals, o25 and o,, Molecular orbitals. ‘Atomic orbitals Molecular orbital isA + 188 ots isA + 1sB ois 28A + 2sB 2s 28A — 2sB 2s 2p.A + 2-8 2p 2p,A — 2p,B 2p 2p,A + 2p,B 72py 2p,/A + 2p,B 72D. 2p,A — 2p,B 2p, 2p,A — 2p,B 22D.18| Vidyalankar : F.E. - Chemistry | Increasing eneray 2 O00¢" : DpO0.0. Pa NR aay ‘Atomic Oritals Molecular Ortitale Atomic Orbitale Fig.: Energy levels of molecular orbitals in diatomic molecules As per modem concept, z axis has been taken as a molecular axis. Thus, p orbitals can form o (sigma) bonds from the frontal overlap of the pz orbitals to form op, and c},molecular orbitals. The p, and py atomic orbitals overlap laterally to form (pi) bonds. Since, this overlap is. lesser than in case of « (sigma) bonds, the x(pi) bonds are weaker than the o (sigma) bonds. The a(pi) molecular orbitals formed are mp, , mpyland m,. 5 Taqy - The relative order of energy of these molecular orbitals is py < Tape ts < Gig < Oe < Hay< Oop < Mon = Ry < Raps = The distribution of electrons in the molecular orbitals is on the basis of Aufbau Principle which states that orbitals of lower energy level will be occupied first by electrons. It also follows Paul's Exclusion Principle, which states that no two electrons in a molecular orbital can have the same quantum numbers. In other words, maximum two electrons can occupy a molecular orbital with opposite spins ( {} ). The Hund's rule of maximum multiplicity is also to be followed for the distribution of electrons in the molecular orbitals. It states that orbitals having the same energy level should have one electron each, with same spin, before pairing takes place. The electronic configuration in the molecular orbital can explain certain facts and the properties observed for a molecule. The following properties can be explained. (i) Stability of the molecular : If Np is the number of electrons present in bonding molecular orbitals and Ng, is the number of electrons occupying anti-bonding molecular orbitals, then (a) the molecule is stable, if Np is greater than Na, i.e. No > Ne, (b) the molecule is unstable, if Ny is less than Na, j/f/INn < Ne-Module 1 : Atomic & Molecular Structure | 19 (ii) Bond order: The bond order (BO) is defined as one half the difference between the number of electrons present in the bonding and anti-bonding molecular orbitals, i.e.,/ Bond Order (BO) = 204 N= A positive BO means a stable molecular. A negative BO or zero BO indicates an unstable molecule. (iii) Number and nature of bonds: The BO values of 1,2,3 corresponds to single, double and triple bonds in molecules. (iv) Magnetic nature : If all the molecular orbitals in a molecule are occupied by paired electrons, i.e/-!doubly occupied ( 4} _), the compound or molecule is diamagnetic. If one or more molecular orbitals are occupied by unpaired electrons, i.e/-/singly occupied ( 7), the molecule is paramagnetic in nature. 1.3.7. Molecular Orbital Diagrams of Some Homonuclear Diatomic Molecules In a diatomic molecule, when both the atoms are the same, ive., /of the same element, it is called Homonuclear. For example, Hz, Hes, Lis, Bez, Bz, Co, No, O2, Fa, Nes, ete. (a) Molecular Orbital Diagram of Bez Molecule The electronic configuration of Be(4) is 1s* 2s*. in a diatomic molecule Bes, there will be a total of eight electrons from two Be atoms, to be filled in the molecular orbitals. The molecular orbital diagram of Bes molecule is shown in Fig. As can be seen in the Fig., the 1s orbital of both the Be atoms, do not take part in the bond formation, i.e.,/they are non-bonding. The remaining 2s orbitals of the two Be atoms combine to form oz. (bonding) and a}, (anti-bonding) molecular orbitals. The four electrons will be filled in both these molecular orbitals as per Aufbau Principle as shown above ,_O_. + Non-bonding Be Bey be ‘Atomic Molecular Atomic orbitals Orbitals Orbitats MO diagrams for Bez molecule The electronic configuration of the molecule Bez can be given as, Bep = KKo?, (6;,)" KK represents the two non-bonding 1s orbitals of two Be atoms. The bond order (BO) of Bez molecule =20| Vidyalankar : F.E. - Chemistry | The zero bond order of Bez molecule suggests that the Be molecule is unstable and does not exist. (b) Molecular Orbital Diagram of O2 Molecule The electronic configuration of O(8) is 1s* 2s* 2p‘. Each oxygen atom has eight electrons. Hence, in O2 molecule, there are sixteen electrons. As 1s orbitals are considered to be non-bonding, the four electrons of 1s orbital of both the oxygen atom can be ignored. The molecular orbital diagram of O2 molecule is shown in Fig. ‘As can be seen from Fig. the non-bonding electrons are ignored. Now, there are twelve electrons in all to be filled in molecular orbitals. As per Aufbau Principle, the next four occupy ozs and a, . These electrons being inner, do not contribute for net bonding. The remaining eight electrons occupy o2p2, pyr Tp, ANG my, aS per Aufbau Principle. Here, degenerate p anti-bonding molecular orbitals ,, and m,,, accommodate one electron each as per Hund's Rule of maximum multiplicity. The electronic configuration of O2 molecules can be given as -y NI as On = KKo%, (635) ape Rap 64(7 op) (7 an) KK represents the two non-bonding 1s orbitals of two O atoms. N,=N, 8-4 2 2 The bond order (BO) of Oz molecule = =2 Incraasing energy ne EGE aren, 2p, 2p, ince(P960/ 2p, Atomic Orbitals Molecular Orbitals ‘Atomic Orbitals Fig.: MO diagram for ©, molecule.Module 1 : Atomic & Molecular Structure _| 21 The bond order os 2 suggests O2 molecule has a double bond (O = ©), one o (sigma) bond and one x (pi) bond between two O atoms. The bond order of 2 also suggests that the O, molecule is quite stable. The presence of two unpaired electrons in its two x (pi) anti-bonding molecular orbitals, 7,,, and ;,,, indicates that Op molecule is paramagnetic in nature. The MOT proved to be successful as Valence Bond Theory (VBT) could not explain the paramagnetic nature of O» molecule. 1.3.8 Molecular Orbital Diagram of Some Heteronuclear Diatomic Molecules In a diatomic molecule, when two atoms belong to different elements, it is called Heteronuclear. For example, CO, NO, HCI, etc. (a) Molecular Orbital Diagram of CO Molecule (Carbon Monoxide Molecule) The electronic configuration of carbon and oxygen atoms can be given as Clo) = 18° 28° 2p” (6) = 1s 2s? 2p* There are total fourteen electrons to be filled in MOs. CO is heteronuclear Molecule in which oxygen is more electronegative than carbon. Therefore, atomic orbitals of oxygen are at lower energy level than the corresponding atomic orbitals of carbon. As the bonding MOs are more closer to oxygen AOs, they contribute more to the MOs. This unequal contribution of carbon and oxygen atoms to the MOs makes CO molecule polar in nature. The molecule of CO (8 + 6) is is electronic with N2 (7 + 7) molecule as both have fourteen electrons. Hence, the molecular orbital diagrams of both are expected to be similar 1s atomic orbitals of C and O are inner, and therefore are non-bonding. Thus, out of fourteen electrons, only ten electrons to be accommodated in the MOs. The molecular orbital diagram of CO molecule which is expected to be similar to No molecule is shown in Fig. eA © ° ‘Atomic Orbitals Motecular orbitals, ‘Atomic Orbitals MO diagram for CO molecule22| Vidyalankar : F.E. - Chemistry | It can be seen in the above diagram that out of ten available electrons, the first four are filled in the bonding o25 and anti-bonding ;, molecular orbitals. The remaining six are filled in three bonding molecular orbitals, pe, Tepy, Ozpe,The electronic configuration of CO molecule can be given as CO = KK (ozs)? (05) (ag) (ne) (apr) (Sane)? where, KK represents the two non-bonding 1s orbitals of C and O atoms. Bond order (80) = No=Ns _ oe = The bond order of 3 indicates that there is a triple bond between C and O (C = 0) one 6 (sigma) and two x!(pi) bonds. As the bond order is 3 which is high CO is a very stable molecule. As all the electrons are paired, CO is diamagnetic in nature. The MO diagrams of No and CO molecules seem almost the same. But there are some differences as evident from their properties. Nz loses an electron on ionization forming Nz" is weaker than in No. (BO of Nz’ = 2.5, and BO of Ne = 3). CO on ionization forms CO" in which, bonding, contrary to the expectations, becomes stronger. This strengthening of bonding in CO” cannot be explained by the above molecular orbital diagram. The correct (improved) molecular orbital diagram can be constructed by taking into consideration, the mixing of atomic orbitals of carbon and atomic orbitals of oxygen atoms, prior to the formation of molecular orbitals. This correct (improved) molecular orbital diagram is shown in Fig. coment \ @ ‘i (Pile 9 (SP,) 0 (sp), (SPdo ¢ co : Fig : Improved MO diagram for CO molecule.Module 1 : Atomic & Molecular Structure _| 23 2s and 2p, orbitals of carbon are assumed to mix and form two non-equivalent orbitals (sp.). with mixed spp character. Similarly, 2s and 2p, orbitals of oxygen are assumed to mix and form two non-equivalent orbitals (spz)o with mixed sp, character. Out of the two (sp). orbitals, one has energy lower than the other. Similar is the case with two (sp.)o orbitals. The atomic orbitals of more electronegative oxygen atom are at lower energy level than the corresponding orbitals of carbon atom. Hence, the lower energy (sp2). orbital of carbon is comparable in energy with the higher energy (sPz)> orbital of oxygen. Therefore, these two orbitals with comparable energy and matching symmetry, overlap and form c bonding and anti-bonding molecular orbitals a(sp.) and o*(spz). The higher energy (spz). and lower energy orbital (sp2)o are far apart from each other. Hence, they do not influence each other and their energies remain almost the same. Therefore, these orbitals can be considered as non-bonding. The degenerate set of 2p, and 2p, orbitals of carbon combine with similar degenerate set of oxygen and form pi, bonding and anti-bonding molecular-orbitals, 2px, Topys Tapxr Tapy From the improved molecular orbital diagram, the new electronic configuration of CO may be written as CO=KK (sp, );, o(SP,) 72 s72P,. »(SP,).2 The non-bonding (Sp). is the highest occupied orbital of CO molecule with electron pair and has highest energy. CO molecule can easily donate this electron pair to form a coordinate bond in coordination compounds like metal carbonyls. Similarly, on ionization, the electron lost will be from this non-bonding (Spz)- orbital. Hence, bond order is not affected, but it reduces interelectronic repulsion causing shortening and strengthening of C=O bond length. (b) Molecular Orbital Diagram of NO Molecule (Nitric Oxide Molecule) The electronie, configuration of nitrogen and oxygen atoms can be given as, There are total fifteen electrons to be filled in MOs. NO is heteronuclear molecule in which oxygen is more electronegative than nitrogen. Therefore, atomic orbitals of oxygen are at lower energy level than the corresponding atomic orbitals of nitrogen. ‘As the bonding MOs are more closer to oxygen AOs, they contribute more to the MOs. This unequal contribution of nitrogen and oxygen atoms to the MOs makes NO molecule polar in nature. The molecular orbital diagram for NO molecule is shown in Fig. There are fifteen electrons to be distributed in various molecular orbitals. 1s atomic orbitals of N and O are inner, and therefore are non-bonding. Thus, out of fifteen electrons only eleven electrons to be accommodated in the MOs. The molecular orbital diagram for NO molecule is similar to that of CO molecule, except that, there is an extra electron in one of the two doubly degenerate (having same energy) anti-bonding 7),. OF 7),,molecular orbital.24] Vidyalankar : F.E. - Chemistry I Nen-bonding « N ° ‘omic Orbials ‘Molecular Oritals——_Atomie Orble Fig. : MO diagram for NO molecule The electronic configuration of NO molecule can be represented as NO = KK 0 (35) Rape? Many? On2” (Ripe) OF (ay) N-N,_ 8-3 Bond Order (BO) = =o -25 2 2 The NO molecule has bond order of 2.5. Since the bond order is less than in Nz molecule (BO = 3), NO molecule is weaker than Nz molecule. Nitric oxide is expected to be less stable due to the presence of an unpaired electron in the anti-bonding molecular orbital. But it is stable. This unusual stability may be due to the charge of the unpaired electron being distributed over both the atoms in a molecular orbital. If the electron had been localized on one atom, then the molecule would have been unstable. On ionization. NO loses one electron and forms nitrosyl ion, NO*. Since single electron from the anti-bonding molecular orbital is removed, the bond order increase from 2.5 to 3. This leads to strengthening and shortening of bond length, as a single bound is longer, double bond is shorter and triple bond is still shorter in length. Thus, NO* gets stabilized and readily forms compounds like NOHSO, (NO* HSO, ) and NOBF, (NO* BF, ) etc. GRADED QUESTIONS What are the fundamental particles of an atom? Explain the concept of shells and sub-shells with reference to the atom. Give graphical representation of sub-shells. What are the orbitals Give the differences between the Orbit and Orbital. What are Quantum Numbers? Explain them in detail.Module 1 : Atomic & Molecular Structure _| 25 10. 1. 12, 13. 14. 15, 16. 17. 18. 19. 20. 21. 24, 25, 26. 27. 28. Explain in detail the following Quantum Numbers : (i) Principal quantum number, (ii) Azimuthal quantum number, (ii) Magnetic quantum number, (iv) Spin quantum number. Give the different shapes of the following orbitals : (i) s-orbitals, (i) p-orbitals, (ii) d-orbitals. What is meant by Electronic Configuration of an element? What are the rules to be followed for filling the electrons? Explain the following rules which have to be followed for filling up of electrons in different orbitals: (i) Aufbau Principle, (ii) Pauli's Exclusion Principle, (ii) Hund's Rule of Maximum Multiplicity. What is Molecular Orbital Theory? Explain LCAO method with reference to MOT. Give diagrammatic representation of the Molecular Orbital Diagram. What are bonding and antisbonding molecular orbitals? How are molecular orbitals formed by addition and subtraction Differentiate between bonding MO and anti-bonding MO. Give difference between bonding and antibonding orbitals [D-19] What are the conditions for the combination of atomic orbitals? What are o (sigma) and x (pi) molecular orbitals. Differentiate between c (sigma) and x (pi) molecular orbitals, Explain the formation of molecular orbitals in diatomic molecules. What are the atomic orbitals which can combine for the formation of a diatomic molecule? What are atomic orbitals? Explain the s-orbitals and p-orbitals [D-19] Give diagrammatic representation of the energy levels of the molecular orbitals in diatomic molecules. What are the properties of a molecule that can be explained on the basis of molecular orbital energy diagram? Explain in detail the molecular orbital diagram for the following Homonuclear Diatomic Molecules : (i) Bez, (ii) O2. Draw the Molecular Orbital diagram of Be2, Give its electronic configuration. Explain why it does not exist. [D-19] Explain on the basis of MOT. Why Bez molecule does not exist On the basis of MOT, explain the bond order and magnetic behaviour of O2 molecule. . Explain on the basis of MOT, why is O2 molecule paramagnetic in nature. . Give the Molecular Orbital diagram of nitric oxide (NO) molecule. [D-19] Explain in detail the molecular orbital diagram for the following Heteronuclear Diatomic Moleculars : (i) CO, (ji) NO. Explain the strengthening of bonding in case of formation of CO* ion on the basis of MOT. . Explain improved (correct) molecular orbital diagram of CO molecule. Explain the bond order and magnetic behaviour of NO molecule on the basis of MOT . Explain why NO ion, nitrosyl ion, is more stable than NO molecule. Explain why NO can readily form compounds like NOHSO, and NOBF,, gogog