Home exercises Quantum chemistry

1. Use the Gaussian 03 program to calculate the potential energy curve of ground state of CO using different quantum chemistry methods such as HF, MP2, MP3 B3LYP, CCSD and QCISD. You can use the 6-31G(d) basis set. Use the scan-keyword to scan R in the range of about [0.75, 4.0]. That is write scan in the route-section and then for the variable: R Rstart nstep dR Where Rstart is the initial R-value, nstep is the number of R-steps in the scan and dR is the step length. See Appendix how to read out the energy, calculated using different quantum chemistry methods. Plot all potentials in the same figure and shift the energy scale to get the minimum of the potentials to agree. Discuss the potential curves calculated using the different methods. When you have done the experiments (home exercise 6) you will add the experimental potential curve to this figure where you use a Morse potential with measured molecular constants. 2. Use the Gaussian 03 program to optimize the CCl4 molecule and study the optimized structure using the MOLDEN program. For the optimized structure run a frequency calculation. Determine the frequencies and study the normal modes using MOLDEN. Also determine the Raman spectrum of the system. You will later compare the calculated Raman frequencies with what you measure in the experiment. Use first the HF/6-31G(d) method and then the B3LYP/6-31G(d) method. 3. The structure of butadiene is given in the figure below. Butadiene is a simple conjugated molecule.

a) What is a conjugated molecule? b) Show how you can use hybrid orbitals to describe the structure of butadiene. What kind of hybrid orbitals do you have to use? c) Use the Hckel molecular orbital theory to determine the molecular orbital energies of the -electrons. (Express the orbital energies in the Coulomb integral and the resonance integral ). Draw a leveldiagram that shows what orbitals are occupied. d) Determine the atomic orbital coefficients for the -orbitals. Discuss how you can use these coefficients to determine whether or not the electrons are localized. e) Use the atomic orbital coefficients for the molecular orbitals to determine the -electron density at each C-atom (EDi) , the total charge density (qi) and the -bond order between the C-atoms.

Appendix Output from the Gaussian Program using different quantum chemistry calculations In general (but not always) in a scan calculation, the energies are summarized at the end of the output file. Hartree-Fock calculation:
SCF Done: E(RHF) = -0.878214160429 Convg = 0.3742D-10 S**2 = 0.0000 A.U. after 4 cycles -V/T = 2.2310

MP2, MP3 calculations:

SCF Done: E(RHF) = -1.05802481891 A.U. after 4 cycles Convg = 0.2998D-08 -V/T = 1.7392 S**2 = 0.0000 Range of M.O.s used for correlation: 1 4 NBasis= 4 NAE= 1 NBE= 1 NFC= 0 NFV= 0 NROrb= 4 NOA= 1 NOB= 1 NVA= 3 NVB= 3 Spin components of T(2) and E(2): alpha-alpha T2 = 0.0000000000D+00 E2= 0.0000000000D+00 alpha-beta T2 = 0.4500573085D-02 E2= -0.1462764682D-01 beta-beta T2 = 0.0000000000D+00 E2= 0.0000000000D+00 ANorm= 0.1002247760D+01 E2= -0.1462764682D-01 EUMP2= -0.10726524657250D+01 R2 and R3 integrals will be kept in memory, NReq= 400110. DD1Dir will call FoFMem 1 times, MxPair= 2 NAB= 1 NAA= 0 NBB= 0. E3= -0.38705718D-02 EUMP3= -0.10765230375D+01

B3LYP:
SCF Done: E(RB+HF-LYP) = -1.13107828928 Convg = 0.1931D-08 S**2 = 0.0000 A.U. after 6 cycles -V/T = 2.2309

CCSD:
SCF Done: E(RHF) = -1.05802481891 A.U. after 4 cycles Convg = 0.2998D-08 -V/T = 1.7392 S**2 = 0.0000 Range of M.O.s used for correlation: 1 4 NBasis= 4 NAE= 1 NBE= 1 NFC= 0 NFV= 0 NROrb= 4 NOA= 1 NOB= 1 NVA= 3 NVB= 3 Estimate disk for full transformation 1044599 words. Spin components of T(2) and E(2): alpha-alpha T2 = 0.0000000000D+00 E2= 0.0000000000D+00 alpha-beta T2 = 0.4500573085D-02 E2= -0.1462764682D-01 beta-beta T2 = 0.0000000000D+00 E2= 0.0000000000D+00 ANorm= 0.1002247760D+01 E2= -0.1462764682D-01 EUMP2= -0.10726524657250D+01 Iterations= 50 Convergence= 0.100D-06 Iteration Nr. 1 ********************** MP4(R+Q)= 0.65832794D-04 E3= -0.38705718D-02 EUMP3= -0.10765230375D+01

E4(DQ)= -0.10047885D-02 UMP4(DQ)= -0.10775278260D+01 E4(SDQ)= -0.10048592D-02 UMP4(SDQ)= -0.10775278967D+01 DE(Corr)= -0.18432383E-01 E(CORR)= -1.0764572016 NORM(A)= 0.10041677D+01

M
Iteration Nr. 8 ********************** DE(Corr)= -0.19839083E-01 E(CORR)= NORM(A)= 0.10042335D+01 Largest amplitude= 5.82D-02 -1.0778639023 Delta=-6.67D-10

CISD:
SCF Done: E(RHF) = -1.05802481891 A.U. after 4 cycles Convg = 0.2998D-08 -V/T = 1.7392 S**2 = 0.0000 Range of M.O.s used for correlation: 1 4 NBasis= 4 NAE= 1 NBE= 1 NFC= 0 NFV= 0 NROrb= 4 NOA= 1 NOB= 1 NVA= 3 NVB= 3 Estimate disk for full transformation 1044599 words. Spin components of T(2) and E(2): alpha-alpha T2 = 0.0000000000D+00 E2= 0.0000000000D+00 alpha-beta T2 = 0.4500573085D-02 E2= -0.1462764682D-01 beta-beta T2 = 0.0000000000D+00 E2= 0.0000000000D+00 ANorm= 0.1002247760D+01 E2= -0.1462764682D-01 EUMP2= -0.10726524657250D+01 Iterations= 50 Convergence= 0.100D-06 Iteration Nr. 1 ********************** E3= -0.38705718D-02 EUMP3= -0.10765230375D+01 DE(CI)= -0.18414911D-01 E(CI)= -0.10764397295D+01 NORM(A)= 0.10041565D+01

M
Iteration Nr. 6 ********************** DE(CI)= -0.19839047D-01 NORM(A)= 0.10042335D+01 E(CI)= -0.10778638663D+01