7. This is so WRONG!

10. -13.6 eV -40 eV -18.6 eV

11. 3s Na Cl (-13.7 eV) Br (-12.5 eV) I F (-18.6 eV) F -

12. -10.6 eV -19 eV -32 eV -15.8 eV

13.  (non-bonding)  (bonding)  (anti- bonding)  (anti- bonding)  (bonding)  (non-bonding)

14. What’s better and worse here?

15. SPARTAN STUDENT MECHANICS PROGRAM: PC/x86 5.0.0 Run type: Geometry optimization (Analytical Gradient) (MM/Amide correction used) Model: RHF/PM3 Number of shells: 4 3 S shells 1 P shells Number of basis functions: 6 Number of electrons: 8 Use of molecular symmetry enabled Molecular charge: 0 Spin multiplicity: 1 Point Group = CNV Order = 2 Nsymop = 4 This system has 2 degrees of freedom Initial Hessian option Hessian from MMFF94 calculation used. Max. Max. Neg. Cycle Energy Grad. Dist. Eigen 1 -221.3325 0.06046 0.00229 2 -223.5289 0.00133 0.00002 3 -223.5364 0.00072 0.00000 4 -223.5370 0.00003 0.00000 Heat of Formation: -223.537 kJ/mol Energy Due to Solvation Solvation Energy -34.383 Semi-Empirical Program CPU Time : 1.53 Semi-Empirical Program Wall Time: 2.10 Use of molecular symmetry enabled Cartesian Coordinates (Angstroms) Atom X Y Z --------- ------------- ------------- ------------- 1 O O1 0.0000000 0.0000000 0.3740089 2 H H1 0.0000000 0.7678384 -0.1870045 3 H H2 0.0000000 -0.7678384 -0.1870045 Point Group = CNV Order = 2 Nsymop = 4

16. Closed-Shell Molecular Orbital Coefficients MO # 1 2 3 4 5 Eigenvalues: -1.35331 -0.64607 -0.53372 -0.45262 0.14921 (ev): -36.82537 -17.5805 -14.5237 -12.3165 4.06018 A1 B1 A1 B2 A1 1 O1 S1 -0.87791 0.00000 -0.33309 0.00000 -0.34397 2 O1 PX 0.00000 0.00000 0.00000 -1.00000 0.00000 3 O1 PY 0.00000 -0.76801 0.00000 0.00000 0.00000 4 O1 PZ 0.10489 0.00000 -0.83472 0.00000 0.54060 5 H1 S -0.33035 -0.45286 0.31008 0.00000 0.54288 6 H2 S -0.33035 0.45286 0.31008 0.00000 0.54288 MO # 6 Eigenvalues: 0.19592 (ev): 5.33138 B1 1 O1 S1 0.00000 2 O1 PX 0.00000 3 O1 PY -0.64044 4 O1 PZ 0.00000 5 H1 S 0.54306 6 H2 S -0.54306 Atomic Charges: Electrostatic Mulliken Natural 1 O1 : -0.709 -0.359 -0.358 2 H1 : +0.354 +0.179 +0.179 3 H2 : +0.354 +0.179 +0.179 Bond Orders Mulliken 1 O1 H1 : 0.968 2 O1 H2 : 0.968

17. bonding Two “O-H bonds” anti-bonding non-bonding Two “lone pairs” but not equivalent!

18. BH3 Closed-Shell Molecular Orbital Coefficients MO # 1 2 3 4 5 Eigenvalues: -0.83413 -0.44511 -0.44511 0.0563 0.08456 (ev): -22.69773 -12.1121 -12.112 1.53242 2.30087 A1' E' E' A2" A1' 1 B1 S1 -0.76782 0.00000 0.00000 0.00000 0.64066 2 B1 PX 0.00000 -0.58025 0.19790 0.00000 0.00000 3 B1 PY 0.00000 0.19790 0.58025 0.00000 0.00000 4 B1 PZ 0.00000 0.00000 0.00000 -1.00000 0.00000 5 H1 S -0.36989 -0.61052 0.20822 0.00000 -0.44330 6 H2 S -0.36989 0.48559 0.42462 0.00000 -0.44330 7 H3 S -0.36989 0.12493 -0.63284 0.00000 -0.44330 MO # 6 7 Eigenvalues: 0.18581 0.18581 (ev): 5.05614 5.05614 E' E' 1 B1 S1 0.00000 0.00000 2 B1 PX -0.13038 0.77919 3 B1 PY 0.77919 0.13038 4 B1 PZ 0.00000 0.00000 5 H1 S 0.08261 -0.49371 6 H2 S -0.46887 0.17531 7 H3 S 0.38626 0.31840

19. Mainly F 2s lcao’s Mainly B 2s-F 2p lcao’s Mainly B 2p lcao’s Note  bonds!

20. Benzene

22. How does the bonding concepts we’ve seen here relate to what you might have seen before, in Organic?

23. F donor (sp) orbitals (6) S valence orbitals (9) a 1g OhOh t 1u a 1g t 1u egeg 3s 3p F. z y x 2p F. Instead of; 3d t 2g egeg Because harder to draw Now, can we tackle bigger molecules, like one with six bonds?

24. F donor (sp) orbitals (6) S valence orbitals (9) a 1g OhOh t 1u a 1g t 1u egeg 3s 3p a 1g t 1u egeg a1ga1g SF 6 F. z y x 2p F. Instead of; 3d t 2g egeg egeg Because harder to draw

26. a1ga1g OhOh t 1u a1ga1g egeg 3s 3p a1ga1g t 1u egeg a1ga1g SF 6 F. Bonding MO’s 8 e- gives 4 bonds! 3d t 2g egeg egeg

27. a1ga1g t 1u a1ga1g egeg 3s 3p a1ga1g t 1u egeg a1ga1g SF 6 Two views: A) 4 bonds distributed over six S-F pairs B) 4 bonds (covalent ) + 2 “bonds” ionic (S 6+ -F - )

30. MO #, Energy, eV Mo(CO) 6 Molybdenum carbonyl Getting Larger: Probably need to use a computer….

31. MO 1 MO 13 MO 22 MO 24

32. MO 39 MO 35 MO 44 MO 50 - LUMO MO 49 - HOMO

33. Sometimes MOs are hard to interpret LUMO HOMO

34. ML4 - D4h M a.o.’s L a.o.’s

35. 3s Na Cl (-13.7 eV) Br (-12.5 eV) I F (-18.6 eV) F -

36. a1ga1g OhOh t 1u a1ga1g egeg 4s 4p ML 6 L : 3d t 2g egeg 6  -donors  ONLY, Like H or NH 3 3rd row M, Valence Atomic orbitals

37. Symmetry Adapted Group Orbitals for 6  -donors

38. a1ga1g OhOh t 1u a1ga1g egeg 4s 4p a1ga1g t 1u egeg a1ga1g ML 6 L : 3d t 2g egeg egeg 6  -donors  ONLY, Like H or NH 3 3rd row M, Valence Atomic orbitals

39. a1ga1g OhOh t 1u a1ga1g egeg 4s 4p a1ga1g t 1u egeg a1ga1g ML 6 L : 3d t 2g egeg egeg 6  -donors  ONLY, Like H or NH 3 3rd row M, Valence Atomic orbitals M-L s bonding MO’s M-L s anti-bonding MO’s

40. a1ga1g OhOh t 1u a1ga1g egeg 4s 4p a1ga1g t 1u egeg a1ga1g ML 6 L : 3d t 2g egeg egeg 6  -donors  ONLY, Like H or NH 3 3rd row M, Valence Atomic orbitals M-L s bonding MO’s M-L s anti-bonding MO’s What is  o?

41. Symmetry Adapted Group Orbitals for 6  -donors

42. a1ga1g OhOh t 1u a1ga1g egeg 4s 4p a1ga1g t 1u egeg a1ga1g L : 3d t 2g egeg egeg 6     -donors Like Cl- 3rd row M, Valence Atomic orbitals M-L s bonding MO’s M-L s anti-bonding MO’s 12 L  orbitals t 1u t 1g t 2g t 2u L..

43. a1ga1g OhOh t 1u a1ga1g egeg 4s 4p a1ga1g t 1u egeg a1ga1g L : 3d t 2g egeg egeg 6     -donors Like Cl- 3rd row M, Valence Atomic orbitals M-L s bonding MO’s M-L s anti-bonding MO’s 12 L  orbitals t 1u t 1g t 2g t 2u t 2g Effect on  o?

44. a1ga1g OhOh t 1u 4s 4p a1ga1g t 1u ML 6 L : 3d t 2g egeg egeg 3rd row M, Valence Atomic orbitals M-L s bonding MO’s M-L s anti-bonding MO’s 12 L  orbitals t 1u t 1g t 2g t 2u 6     -acceptors Like CO, CN- 12 L  orbitals t 1u t 1g t 2g t 2u t 2g a1ga1g t 1u egeg a1ga1g egeg CO

45. 3d t 2g egeg 12 L  orbitals t 2g egeg 3d t 2g egeg egeg oo 3d t 2g egeg egeg 12 L  orbitals t 2g oo oo Case 1. L is  innocent (sigma donor only) Case 3. L is  acid (sigma donor and  acceptor) Case 2. L is  base (sigma donor and  donor)

47. ML4 - D4h M a.o.’s L a.o.’s

48. ML4 - D4h M a.o.’s L a.o.’s d z2 d x2-y2 d xy d xz d yz