chem101/3, wi2010  po    14‐1  chem101/3, wi2010  po    14‐2 

CB VII General
further improvement on Lewis, VSEPR & VB
theory;
Molecular Orbital (MO)
Theory resulting in better info on:
bond energy
bond order
magnetic properties of molecules
........
Ref 11: 3 ........

Prob FUP: 11: 3, 4
E of C: 11: 32 – 37, 51

Adv Rdg 5: 1 - 5

chem101/3, wi2010  po    14‐3  chem101/3, wi2010  po    14‐4 

Basic Principles Basic Ideas
Wave mechanical theory • problem very complex
is applied to bonding in a molecule as a whole
i.e., includes interaction of all nuclei & e–’s • no exact solutions exist

Schroedinger equn is solved for allowed
• various approximations are applied,
wave states, or wave functions, Ψ,
esp. LCAO method
which, in turn, provide a description molecular
(“linear combination of atomic orbitals”)
orbitals (MO’s)

as a result we get a set of discrete MO’s • start off w/ AO’s of bound atoms

describing energy & “location” of e–’s
• generally, combine AO’s that are close in:
important to realize that MO’s cover the molecule proximity,

as a whole (e ’s are “delocalized”), orientation,
rather than being strictly located on or between energy
individual atoms to form MO’s

only the bonding MO. of 2 e–’s per MO. wi2010  po    14‐6  basic ideas . basic ideas .. fill MO’s singly first (w/ same spin) before doubling up chem101/3.of ...chem101/3. σ1s.phase to form bonding MO’s & MO(1). aspects of • apply principles you know from AO Theory wave interference (constructive and destructive) to fill a set MO’s w/ e–’s to construct MO’s as follows: • generally..HB equivalent expression : Energy Diagram MO(1). σ1s out . = antibonding MO’s “Hund” if MO’s are degenerate. • use wavemechanical concepts. wi2010  po    14‐7  chem101/3. AH . wi2010  po    14‐5  chem101/3. “Aufbau” # of MO’s = # of “originating” AO’s in ground state lowest energy MO’s are occupied half of MO’s are lower in energy than “Pauli” the originating AO’s = bonding MO’s max..phase to form antibonding MO’s MO(1) = 1 sA + 1 sB MO(2) = 1 sA – 1 sB 2 e–’s available. wi2010  po    14‐8  Application to H2 Molecule H2 molecule .. if 2 are present .. ∴ H2 stable !! . σ∗1s 1sA & 1sB AO’s combine E 1sB 1sA in . will be filled. esp. they have opposite spins half of MO’s are higher in energy ..

 wi2010  po    14‐11  chem101/3. agrees w/ Lewis theory He2 0 not expected .20 MO Theory for H2 Orbital Diagrams for H2 chem101/3.5 known 2 – 0 B.21 bonding e–’s – antibonding e–’s evaluate for B. Existence for H2: H2+ 0.O.11.chem101/3.O.O. wi2010  po    14‐12  Bond Order by MO Theory Other Row 1 Species General: see Pet. = 2 = 1 ( single bond) He2+ 0. wi2010  po    14‐10  Pet. Fig. 11.5 “expected unknown.O. wi2010  po    14‐9  chem101/3. = 2 species B. and stability: B. in this case. Fig.

 wi2010  po    14‐14  Pet. bonding & antibonding MO’s cancel) i.e. work w/ valence e–’s significant combinations in row 2 orbitals: 2s AO’s σ2s MO σ2p MO 2p AO’s π2p MO chem101/3. wi2010  po    14‐13  chem101/3.23 MO’s from 2p AO’s Combination of p AO’s .chem101/3. wi2010  po    14‐15  chem101/3. homonuclear) Generally. Fig. 11..e. can ignore core AO’s ( i. Fig. 1s AO’s) (because weak interaction.21 MO diagrams for diatomic row 1 species MO Theory for Row 2 Molecules (diatomic. 11.. also. wi2010  po    14‐16  Pet.

N2 Li2.2) σ2s chem101/3.O. wi2010  po    14‐20  General MO Energy Diagram Practice Modified Complete MO Energy Diagrams for valid for Li2 . Ne2 also σ2pz π2px π2py σ∗2s 2s σ2s . wi2010  po    14‐17  chem101/3. B2. wi2010  po    14‐18  MO Energy Diagrams General MO Energy Diagram Expected σ2s lower than σ2p.chem101/3. 14. O2 • fill MO diagrams w/ e–’s HT Fig. F2.14.1) π∗2px π∗2py 2pz 2px 2py π2px π2py but exceptions are common σ2pz σ∗2s “modified” MO diagram 2s (HT Fig. you may want to do 2pz 2px 2py Be2.2 • determine B.. N2.1 expect that σ2p is lower than π2p (σ2p has more overlap than π2p) σ∗2pz “expected” MO diagram (HT Fig. 14. 14. wi2010  po    14‐19  chem101/3. • assess magnetism σ∗2pz π∗2px π∗2py For completeness sake. F2.. C2. (Ne2) (b/c originating 2s AO’s are lower than 2p AO) HT Fig. π2p valid for O2..

 wi2010  po    14‐24  MO Energy Diagram for N2 MO Energy Diagram for O2 σ∗2pz σ∗2pz π∗2px π∗2py π∗2px π∗2py 2pz 2px 2py 2pz 2px 2py σ2pz π2px π2py π2px π2py σ2pz σ∗2s σ∗2s 2s 2s σ2s σ2s 8–4 8–2 B.O. = 2 =1 all e ’s paired ∴ diamagnetic 2 e–’s unpaired ∴ paramagnetic chem101/3.O.chem101/3. wi2010  po    14‐23  chem101/3. = B. = 2 =2 2 =3 2 e–’s unpaired all e–’s paired ∴ paramagnetic ∴ diamagnetic .O. = 2 =1 4–2 – B. wi2010  po    14‐22  MO Energy Diagram for Li2 MO Energy Diagram for B2 σ∗2pz σ∗2pz π∗2px π∗2py π∗2px π∗2py 2pz 2px 2py 2pz 2px 2py σ2pz σ2pz π2px π2py π2px π2py σ∗2s σ∗2s 2s σ2s 2s 2–0 σ2s B. wi2010  po    14‐21  chem101/3.O.

25 provides a summary of MO’s for all row 2 diatomic homonuclear molecules. B. O2– . causing this • similar analysis applies distortion) to row 3 diatomic molecules Na2 ……. 11. wi2010  po    14‐27  chem101/3.3 Combine 3s and 3p AO’s to get σ3s. π3p MO’s (again bonding & antibonding etc.Fig. don’t memorize chem101/3. CO. Fig. NO) • Use the same diagrams to analyze (stability.) .. apply “expected” MO energy diagram. Derive. magnetism …) charged homonuclear species.O. HT Fig.23 Summary of MO theory for row 2 diatomics Summary Pet. when molecule contains O such as N2+. wi2010  po    14‐26  Pet..g. wi2010  po    14‐25  chem101/3. etc. σ3p. wi2010  po    14‐28  Comments Heteronuclear Diatomics (e. but in a “distorted” form (originating AO’s of more e/n atom are lower in energy. 11. Ar2 see CO as an example.14.chem101/3.

 wi2010  po    14‐29  chem101/3. including B. 14. in organic chem.: 6–0 for σ bonds: use VB theory. but often very complicated C O • in many cases. wi2010  po    14‐30  HT Fig. “whatever works best” 2s • e. = 2 =3 hybridization of AO’s all e–’s paired ∴ diamagnetic for π bonds: use MO theory.3 MO Energy Diagram for CO Overall Comment on Bonding • MO theory generally gives best results.g.chem101/3. including resonance ideas from Lewis theory .. simpler theories are satisfactory 2p • “practicing chemists” use a mixture of all theories.O.