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Quantum Chemistry Exercise 3 - Spring 2012

The document outlines the third exercise for an Advanced Quantum Chemistry course in Spring 2012, focusing on many-electron systems and energy calculations. Students are required to compute energy curves for the linear BeH2 molecule using various basis sets and to analyze singlet and triplet states through specific excitation operators. Additionally, it includes tasks related to electronic gradients and transformations between atomic orbital and molecular orbital bases, to be completed by the end of the course.

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Akef Afaneh
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13 views3 pages

Quantum Chemistry Exercise 3 - Spring 2012

The document outlines the third exercise for an Advanced Quantum Chemistry course in Spring 2012, focusing on many-electron systems and energy calculations. Students are required to compute energy curves for the linear BeH2 molecule using various basis sets and to analyze singlet and triplet states through specific excitation operators. Additionally, it includes tasks related to electronic gradients and transformations between atomic orbital and molecular orbital bases, to be completed by the end of the course.

Uploaded by

Akef Afaneh
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Advanced Quantum Chemistry spring 2012, 3rd exercise

The first problem is to be returned in the exercise session, or to the grey metal cabinet in Physicum
before the exercise session. To be discussed in the exercise session on Fri Mar 30 2012 in Physicum
linux class room.

Abstract
We proceed with the introduction to quantum chemistry by examining simple many-electron sys-
tems, paying attention to basis set and correlation effects.

To be done before the exercise session


1. Compute and plot the energy curve of the linear BeH2 molecule at Hartree-Fock level of theory
from RBH = 0.5 Å to R = 10 Å, using the following basis sets:

(a) cc-pVDZ
(b) cc-pCVDZ
(c) cc-pVTZ
(d) cc-pCVTZ

Repeat the calculation using full configuration interaction (FCI). Comment on the differences.
To be solved during the exercise session
2. We consider the total energies of the singlet and triplet states obtained by promoting one electron
from the occupied canonical orbital φi to the virtual canonical orbital φa of a closed-shell Hartree-
Fock state. Using the singlet and triplet excitation operators
1  
0,0
Ŝpq = √ a†pα aqα + a†pβ aqβ
2
1  
1,0
T̂pq = √ a†pα aqα − a†pβ aqβ
2
the total energies of the singlet and triplet states can be written as
D E
1 0,0 0,0
Eai = HF Ŝia Ĥ Ŝai HF
D E
3 1,0 1,0
Eai = HF T̂ia Ĥ T̂ai HF .

(a) Show that the singlet total energy can be expressed as


D E 1D h i E
1
Eai = HF Ĥ HF + HF Eia Ĥ, Eai HF
2

(b) Use
 
h i X X X
Ĥ, Eai |HFi =2 I Fia |HFi +  I
Fba Ebi − I
Fij Eaj + Lbjia Ebj 
b j bj
 
X X
+ gbjca Ebj Eci − gbjik Ebj Eak  |HFi ,
bjc bjk

where I F is the so-called inactive Fock matrix


X
I
Fmn =hmn + (2gmnii − gmiin ) ,
i

to show that the singlet energy may be written in the form


D E
1
Eai = HF Ĥ HF + a − i + 2gaiia − gaaii

(c) Show that the triplet and singlet energies are related as
D E
3 β
Eai =1 Eai − 2 HF Eia α
ĤEai HF

where
α
Eai =a†αα aiα
β
Eai =a†αβ aiβ

(d) Show that the energy of the triplet state becomes


D E
3
Eai = HF Ĥ HF + a − i − gaaii .

2
To be solved and returned by the end of the course
3. The electronic gradient is given by
(1)
Emn =2 (Fmn − Fnm ) ,
where m and n are orbital indices. To go from the AO basis to the MO basis use the equation
X
MO AO
Fmn = Cµm Fµν Cνn .
bfs µ,ν

Solve the problem below.

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