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SHAPES OF MOLECULES (VSEPR MODEL)
Valence Shell Electron-Pair Repulsion model - Electron domains surrounding atom spread out as to minimize repulsion. - Electron domains can be bonding pairs (including multiple bonds) or nonbonding pairs. - Arrangement of all the atoms surrounding central atom depends on electron domains surrounding central atom. Two similar, but different geometries 1. Electron domain geometry - arrangement of e- domain around central atom - remember: multiple bonds count as a single e- domain 2. Molecular geometry - arrangement of atoms around central atom **A molecular geometry is decided only after an electron domain geometry has been determined.** *- need to write Lewis structure to determine number of electron domains.* Geometries with two e- domains about central atom. 1. electron domain geometry – linear A
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A – generic atom

- angle between e domains is 180 ° 2. possible molecular geometries a) Linear - only linear geometry is possible with two electron domains Example: BeCl2 Cl Example: CO2 O C O Be Cl

- Note: Only two electron domains around central atom since multiple bonds count as a single domain. Example: CO O C

2

Geometries with three e- domains about central atom. 1. electron domain geometry – trigonal planar A - angle between e- domains is 120 ° 2. possible molecular geometries a) Trigonal Planar - all three electron domains are bonding pairs Examples: BF3 and NO3F B N F b) Bent (V-shaped) - two bonding pairs and one nonbonding pair Example: dichlorocarbene C Cl Cl O O F O A – generic atom

*Nonbonding e- pairs take up more room than bonding pairs. Therefore bond angle between chlorine atoms is slightly less than 120°.* Geometries with four e- domains about central atom. 1. electron domain geometry – tetrahedral - tetrahedron is three dimensional object - angle between electron domains is 109.4° A Caution! Representation is 2-D, not 3-D, bond angle between epairs is not 90°

2. possible molecular geometries a. Tetrahedral - all four electron domains are bonding pairs Example: CH4 H H C H 2-D picture H

H C HH

H

3-D picture

H H O Example: SF2 S F F . Example: ClO3O Cl O c) Bent (V-shaped) .3 Example: PO43O O P O b) Trigonal Pyramidal .Bond angle is 104.4° because nonbonding pair takes more room than bonding pair. (specifically for NH3) .two bonding pairs and two nonbonding pairs Example: H2O H H O O Cl O O O .3 bonding pairs and 1 nonbonding pair Example: NH3 H N H H O O P OO O N H H H .Bond angle is less than 109. Redraw H2O to show tetrahedral angle.Bond angle is 107°.5°.

equatorial – three positions along equator .domains about central atom. 1. Seesaw . electron domain geometry – trigonal bipyramidal .remember lone pairs prefer equatorial position c.all five electron domains are bonding pairs Example: PF5 F F P F F F F F P F F F Note: axial bond lengths usually longer than equatorial bond lengths b. Trigonal Bipyramidal . T-shaped .angle between equatorial positions is 120° .axial positions are 90° from equator * .four electron domains are bonding pairs and one nonbonding pair Example: SF4 F F F F S F F S F F .nonbonding pairs prefer equatorial position* 2.two different positions in a trigonal bipyramid .4 Geometries with five e.axial – two position along axis . possible molecular geometries a.both lone pairs occupy an equatorial position .three electron domains are bonding pairs and two are nonbonding pairs Example: ClF3 F Cl F F F F Cl F .

) Octahedral .angle between electron domains is 90° 2.five electrons domains are bonding pairs with one lone pair Example: BrF5 F F F F F Br .all three lone pairs occupy equatorial positions Geometries with six e.) Square planar .all six electrons domains are bonding pairs Example: SF6 F F F S F F F b.four electrons domains are bonding pairs with two lone pairs Example: XeF4 F F F Xe F . Linear .) Square pyramidal .domains about central atom.(triiodide ion) I I I . electron domain geometry – octahedral . 1.two electron domains are bonding pairs and three are nonbonding pairs Example: I3.5 d.What are angles between fluorine atoms? . possible molecular geometries a.note angles will be slightly less than 90° c.

BeCl2 is nonpolar molecule and H2O is a polar molecule.6 POLAR MOLECULES A polar molecule has one side slightly positive and the other slightly negative. Question: How can this be? Answer: BeCl2 has a linear geometry and H2O has a bent geometry.) Correct geometry To emphasize necessity of correct geometry. however.) Polar covalent bonds 2.5 |χH – χO| = 1.0 |χBe – χCl| = 1. H Cl Be Cl δ+ O δtotal polarity adds to zero total polarity is nonzero H H2O χH = 2.1 χO = 3. but methane is a nonpolar molecule. compare two examples.5 χCl = 3. .4 δ+ δH–O Example: Is either ammonia or methane a polar molecule? δ- H C HH H N H H H δ + Answer: Ammonia is a polar molecule. 1. BeCl2 χBe = 1.5 δ+ δBe – Cl indicates positive end of bond Be – Cl bond is more polar than H – O bond. Two conditions must be met in a polar molecule.

Bond is overlap of two 2pz orbitals. VALENCE BOND THEORY Bond Overlap Molecular bonds form when atomic orbitals overlap. it has a dipole moment. the dipole moment is defined as µ=Q×d Since a polar molecule has a separation of charge. F F C F F Cl F C F F Dipole Moment . . Polarity of molecule is usually considered via its dipole moment.µ When equal and opposite charges. d. Hydrogen Fluoride – HF 2pz 1s 2pz . ±Q. are separated by a distance.7 Nonequivalent polar bonds can affect overall polarity. Fluorine – F2 2pz .Bond is overlap of two 1s orbitals. CF3Cl is a polar molecule.Bond is overlap of a 1s orbital and a 2pz orbital. CF4 is a nonpolar molecule. Hydrogen – H2 1s 1s .

Potential Energy Curve for Diatomic Bonding Energy nuclear repulsion electron overlap zero interaction at R = ∞ Atomic Distance [R] Equilibrium bond length HYBRIDIZATION Consider the orbital diagram of the ground state carbon atom. Nuclei start to repel each other. .As atoms approach each other.8 Concepts of bond overlap . increasing overlap has a limit. 2p 2s 1s Since bonding occurs from the overlap of atomic orbitals. . How can this be? . one would naïvely think that the carbon would form only two bonds coming from the overlap of the two 2p electrons with orbitals from other atoms. we know (from a huge number of experiments) that carbon forms four bonds. However.Bond distance is a compromise between increasing overlap and increasing nuclear repulsion.Energy of molecule is lowered when overlap of singly occupied orbitals occurs.

3 bonds from the overlap of carbon 2p orbitals and hydrogen 1s orbitals . there is a boatload of experimental evidence demonstrating the equivalence of all of the bonds. 2sp3 1s The shape of an sp3 is a lopsided dumbbell. In a compound such as methane. There is no way to differentiate between the four bonds. CH4. we have another problem. -Again.e.. all the bonds surrounding the carbon atom are identical. we invoke the concept of hybridization.9 Perhaps a small input of energy causes one of the 2s electrons to enter the empty 2p orbital. All four sp3 orbitals point a different corner of a tetrahedron. blend. together to form four identical orbitals. . how can this be? We should have . 2p 2s 1s Now the carbon atom can form four bonds. Once again. The three 2p orbitals and the one 2s orbital hybridize. however. i.1 bond from the overlap of a carbon 2s orbital and a hydrogen 1s orbital To rationalize the fact that all of the bonds are equivalent. labeled in this specific case as sp3 orbitals.

Electron domain geometry Linear Trigonal planar Tetrahedral Trigonal bipyramidal Octahedral Number of identical orbitals 2 3 4 5 6 Hybridization of atomic orbitals sp sp2 sp3 sp3d sp3d2 Example: What is the hybridization of the valence orbitals of the boron atom in BF3? F B F F 3 e.first covalent bond between atoms . NCl5 can’t exist because there is no 2d orbital! COVALENT BOND ORBITALS (sigma and pi bonds) Sigma bonds .10 Thus there exists an intimate connection between the electron domain geometry of an atom and the hybridization of the orbitals on that atom. why can’t NCl5 exist? A: The sp3d orbitals come from blending one 3s. Q: If PCl5 can exist. Hybridization of Expended Octets The phosphorus atom in PCl5 can “expand its octet” to form a trigonal bipyramidal shape with sp3d hybridized orbitals.strongest covalent bond F2 σ bond from overlap of 2p orbitals .domains Æ Tetrahedral Æ sp3 hybridization Example: What orbitals are overlapping to create the covalent bonds in BF3? 2sp2 orbital of boron overlapping with 2sp3 orbital of fluorine.σ . three 3p and one 3d orbitals.bond is directly between nuclei H2 σ bond from overlap of 1s orbitals .domains Æ Trigonal planar Æ sp2 hybridization Example: What is the hybridization of the valence orbitals of the fluorine atoms in BF3? 4 e.

Examine bonding is acetylene.also triple bonds . extra bonds after sigma bond .Two π bonds means each carbon is using two p orbitals for π bonds. therefore.consider carbon monoxide O C 1 σ C – O bond 2 π C – O bonds 11 2 σ C – H bonds . Reexamine bonding in formaldehyde O C H H Q: What is hybridization of carbon orbitals? A: One p orbital is used in formation of π bond. . hybridization is sp.double bond.Note: hybridization matches linear geometry. C2H2 H–C≡C–H .Bond is outside of internuclear axis. . C O π bond – both parts belong to one pi bond.Two π bonds are perpendicular to each other. . other orbitals hybridize to form sp2 orbitals.Bond comes from overlap of perpendicular p orbitals.π . . therefore.Note: sp2 hybridization is consistent with trigonal planar geometry.consider formaldehyde O 1 σ C – O bond C 1 π C – O bond H H .Pi bonds . .Pi bonds are weaker than sigma bonds. .

Pi bond is delocalized over both C – O sigma bonds. . HCO2O H C O .Resonance always indicates delocalization of bonds.12 RESONANCE AND DELOCALIZATION Consider resonance of formate ion. H C O O O σ H σ C π σ O .

Two waves add together to destroy each other.effect of antibonding orbital slightly greater than bonding orbital . 1. Antibonding orbitals – σ*. π . mixing) occurs.when filled with e-.result of constructive interference .85 2.antibonding orbitals have node between nuclei . Destructive interference .result of destructive interference .85 20 Molecular Orbitals When two atomic orbitals are put together. two types of interferences (i. π* . they draw atoms together. they push atoms apart .When two waves are put together.13 MOLECULAR ORBITAL THEORY Wave Interference .when filled with e-. and two molecular orbitals result. Constructive interference .electron density decreases between atoms . Bonding orbitals – σ. they interfere with each other.975 2 0 0 2 4 6 8 10 x 12 14 16 18 20 18.5 1 1 0 0 2 4 6 8 10 x 12 14 16 18 18. .electron density increases between atoms 2.always higher energy than similar bonding orbital .5 f( x ) h ( x ) f( x ) h ( x ) 0 0. 1. 1.Two waves add together to reinforce each other. e.975 2 1 f( x ) g( x ) f( x ) g( x ) 0 1 1. 1 1 0.

14 Molecular orbitals (MO) of H2 ⇒ 1s σ bonding orbital + + 1s σ* antibonding orbital 1s 1s Molecular orbital diagram of H2 1s σ* 1s σ* 1s 1s 1s 1s 1s σ 1s σ Note one bonding orbital is filled. therefore. bond order is zero. therefore. Bond order = ½(# of bonding e. bond order is one. bond order is ½.– # antibonding e-) Molecular orbital diagram of He2 1s σ* 1s 1s 1s σ One bonding orbital and one antibonding orbital are filled. Molecular orbital diagram of He2+ or H21s σ* He2+ exists!! However the atoms are lightly bonded together. 1s σ . therefore. 1s 1s Two bonding eand one antibonding e-.

Though not as crystal.As a consequence. Be2 does not exist. 1s and 2s orbitals do not mix together very much. Molecular orbitals from p orbitals Sigma orbitals constructive interference + 2p destructive interference – 2p Pi orbitals constructive interference 2p ⇒ 2p σ* destructive interference 2p ⇒ 2p σ + ⇒ 2p π – ⇒ 2p 2p 2p 2p 2p π* . only as gas. . Note: Two atomic orbitals making two molecular orbitals must be close in energy.15 Molecular orbital diagrams of Li2 and Be2 Li2 Be2 2s σ* 2s σ* 2s 2s 2s 2s 2s σ 2s σ 1s σ* 1s σ* 1s 1s 1s 1s 1s σ 1s σ Bond Order = 2 bonds – 1 antibond = 1 Bond Order = 2 bonds – 2 antibonds = 0 Li2 exists.

F2.16 MO Diagrams of O2. Ne2 2p σ* 2p π* 2p 2p π 2p σ 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s 1s σ .

N2 2p σ* 2p π* 2p 2p σ 2p π 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s 1s σ . Magnetic Molecules Diamagnetic .in fact. C2.2s and 2p orbital hybridize causing σ and π orbitals to be “out of order” Using MO Theory to predict bonding and magnetic properties One of the great successes of MO theory is that it correctly predicts the magnetic properties of diatomic molecules.molecule with unpaired e.molecule behaves as if it is magnet.spinning e. it is attracted to other magnets .acts like bar magnet .e.17 MO Diagrams of B2.molecule not attracted to magnet .molecule with no unpaired e.has magnetic moment . slightly repelled by magnet Paramagnetic .

18 MO Diagrams of B2 2p σ* 2p π* 2p 2p σ 2p π 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s B2 is paramagnetic Bond order = 1 MO Diagrams of C2 1s σ 2p σ* 2p π* 2p 2p σ 2p π 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s 1s σ C2 is diamagnetic Bond order = 2 .

19 MO Diagrams of N2 2p σ* 2p π* 2p 2p σ 2p π 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s 1s σ N2 is diamagnetic Bond order = 3 MO Diagrams of O2 2p σ* 2p π* 2p 2p π 2p σ 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s 1s σ O2 is paramagnetic Bond order = 2 .

20 MO Diagrams of F2 2p σ* 2p π* 2p 2p π 2p σ 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s 1s σ F2 is diamagnetic Bond order = 1 MO Diagrams of Ne2 2p σ* 2p π* 2p 2p π 2p σ 2p 2s σ* 2s 2s 2s σ 1s σ* 1s 1s Ne2 does not exist Bond order = 0 1s σ .