 Lewis Structures

o VSEPR: lp>mb>sb
o Resonance contributors: expanded octet (min. charge sep) – octet (charge sep)
o No bond resonance for F only
o Don’t expand octet B thru F
 Symmetry
o C vs. D
o Element = point, plane, axis
o Cn rotations, reflections (v,d,h)
o Improper rotations: Sn
o Identity: E
 Character tables
o Point group Symmetry classes Functions (axes, orbitals, quadratics)
o Properties
 Symmetry class: all have identical characters
 Each row = irreducible representation
 # classes = # irreducible representations
 Order(h) = total # symmetry operations
 h=sum(dimension)^2 = (character^2*class coefficient) for particular
irreducible representation
 Orthogonality of characters (multiply by class coefficient too)
o Mulliken labels
 Dimension under E
 A: symmetric wrt 1st symmetry operation
 B: antisymmetric
 E: 2-D (x,y) under C3 symmetry
 T: 3-D (x,y,z) transform as T2 in tetrahedral symmetry
 Superscripts
 A’ symmetric wrt sigmah
 A’’ antisymmetric
 Subscripts
 A1 symmetric wrt secondary symmetry operation
 A2 antisymmetric wrt secondary symmetry operation
 A3, etc. if degeneration operations
 Ag symmetric wrt inversion
 Au antisymmetric wrt inversion
 MO diagrams algorithm
o Assign point group
o Prearrange satellite atoms’ orbitals to match symmetry of central atom
o Find reducible representation for equivalent ligands – label positions that will be
exchanging, perform sym op, identify positions that stay put (all or nothing) ->
chi =1 or 0 for each atom; sum together
o Reduce reducible representation: a1*( )+a2*( )+…
o Figure out what SALCs do, look at bonding interactions w/ central atom
  Projection operators: list all sym ops, transform 1 atom of set under each
op, multiply by character
 Expression: 1/sqrt(nc)*(nA1+mA2…)
 OK: use solutions to problems you already know
o Draw MO diagram – if symmetric, combine SALCs; if asymmetric, hybridize
AOs on central atom
o Greater population of orbitals -> bond order analysis
 B.O.= # filled bonding MO - # filled antibonding MO
 Need to be able to draw and identify bonding/antibonding character
 Apply symmetry analysis to vibrational modes
 IR, Raman selection rules from C.T. (quadratic, axis)
o Small HOMO-LUMO gap: greater reactivity
o Either raise HOMO or lower LUMO to increase reactivity
o