Experiment 8

TITLE

: Binding Energy, Ionization Potential, Electron Affinity

Objectives

1. To understand the ionization potential (IE), the electron affinity (EA), and the binding
energy (BE).
2. To calculate the IE and the EA using both Koopman's Theorem and Direct SCF method.
3. To determine the binding energy
Introduction
All GAMESS calculations that you performed until now was done using the HartreeFock (HF) method. HF method is a reasonable model in many problems particularly in
providing reliable predictions for geometries of molecules. However, the limitation is that the
theory does not include electron correlation. For many molecular systems such effect is very
critical for determining the energetics and properties of molecular systems, particularly in
calculating the energetics of reactions and bond dissociations. In this experiment, we will study
the ionization potential, the electron affinity, the binding energy, and the Koopman's theorem.
Ionization energies (IE) measure the tendency of a neutral atom to resist to the loss of electrons.
Thus, it takes a considerable amount of energy. While the electron affinity (EA) is the energy
given off when a neutral atom in the gas phase gains an extra electron to form a negatively
charged ion.
As you already know frontier orbitals are a collective term for the Highest Occupied
Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO). We use the
approach known as "Koopman's theorem". Based on the "Koopman's theorem" IE is equal to the
Highest Occupied Molecular Orbital (HOMO) energy (this method is exact for only hydrogenic
atoms) and the EA is the energy of the Lowest Unoccupied Molecular Orbital (LUMO)
approximately. Thus, the Koopman's Theorem takes the minus of the energy of the HOMO for the
ionization energy and the eigenvalue of the LUMO for the EA (no sign change).
We can also use the "Direct SCF method" or the "subtraction method" in which the IE is
equals to the energy of the ion minus the energy of the neutral form of the molecule and the EA is
the energy of the neutral form and the anionic form of the molecule. Therefore, the binding energy is
defined as;
Binding Energy (BE) = [ E(Monomer 1) + ZPE(Monomer 1) ] + [ E(Monomer 2) +
ZPE(Monomer 2) ] - [ E(Dimer) + ZPE(Dimer) ]

Precedure

1. Calculating the properties of PH2, PH2+, and PH2An optimization job on the structures and also a hessian calculation
was run to get the zero point energy correction factors

It was compared with experimental values

The results was recorded in the following tables.

2. Binding Energy in HF
An energy calculation for HF, H, and F was run for each method
separately used the basis set mentioned in the following table.

The energy of the HF molecule was adjusted to get the zero point
energies which can be provided by their hessian calculation.

The binding energy for each computational method was calculated

and compared with experimental binding energy value (141.2
kcal/mol). The results was recorded in the following table.

Result

1. Calculating the properties of PH2, PH2+, and PH2coordinate

Charge
Multiplicity
wavefunction
Basis set
Vibrational scaling
factor

PH2
cartesian
0
2
ROHF
6-31G(2d,p)
0.856

PH2cartesian
-1
1
RHF
6-31G++(2d,p)
0.904

PH2+
cartesian
+1
3
ROHF
6-31G(2d,p)
0.856

Table 1: Ionization Energy (Reference experimental IE of PH2 = 9.82 eV or 226.45 kcal/mol)

Molecule

PH2
PH2+
PH2-

Koopmans` theorem IE
-HOMO(opt)
LUMO(opt)
-0.1563
---

E(Hartree)(opt)

0.1592
---

SCF IE
ZPE(Hartree)
(Hessian)
0.014379
0.012384
0.012434

Table 2: Electron Affinity (Reference experimental EA of PH2 = 1.26 eV or 29.06 kcal/mol)

2. Binding Energy in HF

HF/STO-3G

HF/631G

HF/631G(d)

E(H)
(Hartree)

E(F)
Hartree

E(HF)
(Hartree)

0.4665818
504
0.4982329
092
0.4982329
092
-0.4982329
092

97.9865050
330
99.3602181
659
99.3617921
172
99.3622294
747

98.55462715
09
99.96150596
32
99.97622049
05
100.0176288
450

0.4998098
153
0.4998098
153

99.3976089
299
99.3983077
787

100.0242199
102
100.0248046
200

HF/631G(2d,p)

HF/6311+G
(2d,p)
HF/6311+G
(2df,p)

ZPE(H
F)
(Hart
ree)
0.0101
95

B. Energy
(Hartree)

0.0094
21

0.0936338
849

0.0099
28

0.0936338
849

0.0102
39

0.1674054
611

0.0102
05

0.1165970
65

0.0103
09

0.1163780
14

0.0913452
675

B.
Energy
(Kcal/
mol)

MP2/6311G(2d,p
)
MP2/6311+G
(2d,p)

0.4998098
153

-0.4998098
153
MP2/6311+G(2df ,pd)
0.4998098
153

99.3949092
786
99.3976089
299
99.3983077
787

100.0176288
450
100.0242199
102
100.0248046
200

0.0096
31

0.1132787
14

0.0095
09

0.1172921
65

0.0095
52

0.1171350
26

Question ( Part 1)
i.

Compare the calculated results with the experimental values. What is your conclusion?

ii.

Compare the results of these two different methods. Which method provides a better
prediction?

iii.

What are the fundamental differences between these two methods?

Question (Part 2)

i.

What basis set provides the most accurate results? Why?

ii.

Compare your calculated results with the experimental value. Determine the error (in
kcal/mol) with respect to the experimental value for each calculation and fill out the table
below;

HF/STO-3G
HF/631G
HF/631G(d)
HF/631G(2d,p)
HF/6311+G (2d,p)
HF/6311+G (2df,pd)

MP2/6311G(2d,p)
MP2/6311+G (2d,p)
MP2/6311+G (2df,p)
MP2/6311+G(2df,pd
)

Discussion

Conclusion

References
1. Atkins, P. & de Paulo, J. (2009). Physical Chemistry. 9th edition. Oxford: Oxford University
Press.
2. http://www.sparknotes.com/chemistry/organic2/conformations/section1.rhtml
3. http://chemwiki.ucdavis.edu/Physical_Chemistry/Spectroscopy/Vibrational_Spectroscop
y/Vibrational_Modes
4. https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/rotconf1.htm