PHYS 583 A/MSE 583C

Computational Materials Physics

Report 1: ORCA Quantum Chemistry Calculations
09/22/2020

Daviti Gochitashvili
Binghamton Univeristy

Introduction
In this report there will be considered some basic, but very important examples of working
in Quantum Chemistry Calculations. All the calculations are performed on ab initio program
ORCA and visualizations are made using Avogadro software. Report consists of six tasks,
which covers various method of Geometry optimizations/Structure relaxations, Vibrational
frequency calculations, Potential energy scannig, transtions state observations of chemical
reactions. All the code was running on Open High Performace Computer Server of
Binghamton University.
 Task 1: Hartree-Fock on H2 molecule

1) HOMO and LUMO of H2 Molecule:

Figure 1 HOMO -16.389 (eV) Figure 2 LUMO 5.538 (eV)

2) The first frequency considered to be a vibration is 5 with frequency 4589.34

cm-1

The total number of vibrations considered is 1. Vibrations are directed along the
the bond and move like shown with arrows.

3) Plots of Energy vs Distance for Singlet and tiplet states

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4) Total energy of the H2 Molecule: -30.71971 eV. As 2 H atoms will apart from each other each will
have energy of -13.6 eV. So molecule will have more energy.

5) Hund’s rule tells us: “For a given electron configuration, the term with maximum multiplicity has
the lowest energy.”.

Task 2: Hartree-Fock on H2O

1) Bond length between H and O is 0.99 Å. and angle between H-O-H 104.5°.

2) 3 modes are present with frequencies:

6: 1750.34 cm-1

7: 4148.56 cm-1

8: 4244.63 cm-1

The first frequency considered to be a vibration is 6

The total number of vibrations considered is 3

Figure 4 H atoms stretch and compress Figure 3 H atoms move up and down Figure 5 H atoms stretch and compress
along the bonds symmetrically like butterfly wings asymmetrically along the bonds.

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3) The bond stretching energy (frequency) is more then bond bending in all three vibrational modes
as we can see from experiment.

Task 3: HOOH

1)

2)

3) From this vibrations we can see, that twisting frequencies are less than the stretching and bending.

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 Task 4a: Basis sets on H-atom

1) Real is -0.5 Hartree.

Basis Set STO-3G 3-21G 6-31G 6-311G 6-311G(d,p) cc-PVDZ

Energy -0.46658185 -0.49619861 -0.49823292 -0.49980981 -0.49980982 -0.49927840
(Hartree)
Basis Set cc-PVTZ cc-PVQZ cc-PV5Z cc-PV6Z
Energy -0.49994532 -0.49980759 -0.49999431 -0.49999920
(Hartree)

2) As we can see from the table above, STO-3G has lower accuracy beacause is it simple combinations
of Gaussian functions. Pople basis sets are more accurate. Correlation-consistent basis sets seems to be
closest to the real value.

Task 4b: Basis sets on the protonation of water

Basis Set STO-3G 6-31G 6-311G 6-311G(d) 6-311G(d,p) 6-311+G(d,p)
Energy -75.3180 -76.2655 -76.2939 -76.3116 -76.3276 -76.3280
(Hartree)

Task 4c: Basis Set Superposition Error

In the approach with functions, we linear combinations of them. Of course because of superpositions
and overlaps sometimes can cause errors in calculations.

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 Task 5: Benzene
1)

Method name HF LDA PBE B3LYP

Total Enegy -230.75677384 -230.15417558 -231.99518698 -232.15691615
(Hartree)
HOMO energy -9.2056 -6.5601 -6.3241 -6.9922
(eV)
LUMO energy 1.9059 -1.4114 -1.2553 -0.4138
(eV)
HOMO-LUMO -11.1115 -5.1487 -5.0688 -6.5784
gap (eV)
C-C bond length 1.076 1.095 1.041 1.110
(Å)
C-H bond length 1.386 1.389 1.093 1.521
(Å)

2)
-13.522 eV -9.206 eV -9.206 eV

1.906 Ev 2.157 Ev 2.157 Ev

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 Task 6: SN2 Reaction Barrier – Transition State calculation
1) The illustation shows 2 minima. Diffrenece between these 2 energies is 0.02129 eV.

-3071.100736eV -3071.079445 eV

2) Reaction barrier is -3071.06912 eV.

TS

------------------------------------------------
6: -314.82 cm**-1 ***imaginary mode***
7: 165.13 cm**-1
8: 171.33 cm**-1
9: 172.10 cm**-1
10: 870.12 cm**-1
11: 870.98 cm**-1
12: 997.06 cm**-1
13: 1400.92 cm**-1
14: 1402.50 cm**-1
15: 3185.95 cm**-1
16: 3382.15 cm**-1
17: 3383.89 cm**-1
------------------------------------------------

Reactant Transition State Product

Cl—C distance (Å) 2.563 2.423 1.200
Br—C distance (Å) 2.202 2.475 3.827
Reaction (eV) -3071.10073 -3071.06912 -3071.07944