1 Chemistry - Assignment VII - 2013 1.

A teacher and a student used dierent co-ordinate systems, to construct their own sets of p-orbitals. The axes chosen by the student is indicated with a prime. The Z- axes of both coincide, while the X and Y-axes are obtained by a rotation about the Z-axis by 45o . What are the expressions for px and py in terms of px and py ? If there is one electron in each of the orbitals, show that the electron density calculated using either set is the same. 2. The molecule BCl3 is a planar molecule that has the shape of an equilateral triangle with three equivalent bonds. This may be explained by the hybridization of the 2s with two of the 2p orbitals. Assuming the p orbitals to be 2px and 2py construct three equivalent hybrid orbitals, that lie in the XY plane. 3. In CH4 one has sp3 hybridization. The hybrid orbitals can be taken to be: 1 (2s + 2px + 2py + 2pz ) 2 1 2 = (2s + 2px 2py 2pz ) 2 1 3 = (2s 2px + 2py 2pz ) 2 1 4 = (2s 2px 2py + 2pz ) 2 1 = Discuss the shapes and orientation of these hybrid orbitals. 4. Lookup H uckel MO theory in the book Molecular Orbital Theory for Organic Chemists by A. Streitwieser, John Wiley and sons, Inc, 1961 and (a) apply it to allyl system. (b) Using the expressions for HMOs (from the book by Streitwieser), calculate the resonance energies for cyclobutadiene and benzene.