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Hyper Chem Car Bocatio Nex PT
Hyper Chem Car Bocatio Nex PT
Prof. T. Nalli,
As directed in Pavia, we will be doing semi-empirical MO calculations using the AM1 parameter set. Set up Hyperchem to do this by selecting Semiempirical under the Setup menu and then AM1. To compute the energy of each molecule once built, select Geometry Optimization under the Compute menu and then OK. (An RMS gradient of 0.01 and the Polak-Ribiere energy minimization algorithm should both work fine for our purposes.) The energy displayed by the program once the calculation is completed represents the Standard Enthalpy of Formation of the molecule in kcal/mol. Suggested Procedures 1. Calculate the energy of each of the four alkyl bromides in turn. Save each molecule once the calculation is complete (you will need them later) and then create the next one by replacing one H with a CH3. 2. Now calculate the energy of the carbocations. Pull up each saved RBr file in turn and first remove the bromine atom (right click on it). Under Build, choose Explicit Hydrogens and Allow Arbitrary Valence. Then go to the Setup menu and select Semi-empirical, Options. This is where you set the charge to +1. Also set the spin multiplicity to 1. Calculate the energy of the carbocation using Geometry Optimization as before. (Also note your observations on the geometry of the optimized carbocation.) (Also save each carbocation file before going on to the next calculation!) 3. Lastly, compute the energy of a bromide ion. Set the charge to 1 in the same manner as in step 2. Part 2 (Expt 19B, Part 2) Solution Phase SN1 (H2O Solvent) For this part, we will need to repeat all of the calculations of part 1 but this time including a surrounding matrix of water molecules. In Hyperchem, this is accomplished by placing the molecule in a defined box. First reopen the file for the structure to be calculated. Then under Setup, choose Periodic Box. Set the periodic box dimension for all directions to nine angstroms. Now, as before compute the energy using Geometry Optimization. Set the maximum number of cycles to 250. The calculations will take some time- be patient. Part 3 (Expt 19D, Part 1) Carbocation Electrostatic Potential Maps Unfortunately, Hyperchem 7.5 no longer allows the generation of electrostatic potential maps that can be compared meaningfully from molecule to molecule. Specifically it will not allow the setting of color values (as described in Pavia) to the same range for the four carbocations to be examined. (Hyperchem now automatically determines the range of color values to be used for each molecule). Suffice it to say the maps would come out exactly as pictured on p 249, Fig 7.17 in Smith. No matter, what we will do is betterobtain quantitative predictions of the charge on each carbon
Reopen each carbocation structure from part 1. Under the Display menu select Labels. Under Atoms select charge. Record the charge of each carbon atom as data in your notebook. Pay special attention to the charge on the carbocation carbon, i.e, the carbon with formal charge = +1.
Part 4 (Expt 19D, Part 2) Allyl Cation Electrostatic Potential Map Build and optimize the allyl cation, CH2=CH-CH2+, using the techniques learned earlier in the lab. Note your observations on the optimized structure and then display and record the atomic charges using the same procedures as in part 3 above.