Particle in A Box Revisited-TFG Borja Rodrigo

Jaume I University
Chemistry Degree
Bachelor’s Degree in Chemistry
Higher School of Technology and Experimental Science

Department of Physical Chemistry
Castellón de la Plana, Spain
Particle in a Box Revisited
Author:
Borja Rodrigo Romero
Mentor:
Fernando Rajadell
July 2018
Index
1. Abstract ......................................................................................................................................... 1
2. Introduction .................................................................................................................................. 1
2.1. Particle in a Box without Potential ......................................................................................... 1
2.1.1. Particle in a One-Dimensional Box ........................................................................ 1
2.1.2. Particle in a Two-Dimensional Box ........................................................................ 4
2.2. Particle in a Box with Potential .............................................................................................. 7
2.2.1. Linear Variations Method ...................................................................................... 7
2.2.2. Nondegenerate Perturbation Theory ..................................................................... 8
2.3. Radiation/Matter Interaction ................................................................................................ 10
3. Results......................................................................................................................................... 11
3.1. Approximation by Linear Variation Method ......................................................................... 13
3.1.1. Particle in a 1D System with 𝑉 ≠ 0 inside the Box ............................................. 13
3.1.2. Particle in a 2D System with 𝑉 ≠ 0 inside the Box ............................................. 15
3.2. Approximation by Perturbation Theory Time-Independent.................................................. 17
3.2.1. Particle in a 1D System with Perturbation inside the Box .................................... 17
3.2.2. Particle in a 2D System with Perturbation inside the Box .................................... 18
3.3. Selection Rules of Transitions ............................................................................................ 20
3.4. Comparative Results between approximated Methods and COMSOL ............................... 21
4. Discussion .................................................................................................................................. 23
5. Annexes....................................................................................................................................... 25
6. References .................................................................................................................................. 77
Physical Chemistry
1. Abstract
Some important concepts will be introduced on quantum chemistry such as symmetry labels of molecular
states by dwelling on the “particle in a box” model. The mathematical models introduced allow
understanding orthogonality relationships, expansion of an orbital in a complete set of basis functions,
perturbation theory of nondegenerate energy levels, and transition probabilities with some attention to
selection rules. This project is developed by means of Mathematica and COMSOL codes in an
experimental laboratory.
2. Introduction
In the present work we will evaluate the particle in a one-dimensional and two-dimensional box. For both
situations we will study the addition of a potential whose effect, on the energy and wave functions, will
analyzed by two approximation methods: 1) Linear variation method and 2) Perturbation theory time-
independent. The results obtained will be contrasted with an “exact” numerical method. This method will
carried out through COMSOL code in finite elements. We will also make reference, succinctly, to the time-
independent perturbation theory meaning to introduce the transition dipole moment to pay attention to
radiation-matter interaction evaluating the probabilities transitions between energy levels of particle in a
box. With aim to simplify the algebra of formula used, we will use u.a.(atomic units).
2.1 Particle in a Box without Potential
The stationary-state wave functions and energy levels of a one-particle are found by solving the time-
independent Schrödinger equation. The model of the particle in a box has a perfect extension to one, two
or three dimensions.
2.1.1 Particle in a One-Dimensional Box
This is a simple system model where a particle is subjected to a potential-energy function that is infinite
everywhere along the 𝑥 axis except for a line segment of length 𝑎, where the potential energy is zero. In
this case, the box is centered at the origin of coordinates.
∞ ∞
𝑉 𝑥 𝑉 𝑥 =0
𝑥 = −𝑎/2 𝑥=0 𝑥 = 𝑎/2

Figure 1. Particle in a one-dimensional box −𝒂/𝟐 ≤ 𝒙 ≤ 𝒂/𝟐.
1
Physical Chemistry
It has assumed throughout this work that the particle has a mass, m, 1 u.a. The length of the box is from
𝑥 = −𝑎/2 to 𝑥 = 𝑎/2, where 𝑎 = 1 u.a. As usual, an infinite potential is invoked on the two extremities of
the box. Thus, the set of normalized eigenfunctions satisfying the basic axioms of quantum theory are
2 𝑛𝜋𝑥
𝛹𝑛 = √ 𝑐𝑜𝑠 𝑛 = 𝑜𝑑𝑑 1
𝑎 𝑎
2 𝑛𝜋𝑥
𝛹𝑛 = √ 𝑠𝑖𝑛 𝑛 = 𝑝𝑎𝑖𝑟 2
𝑎 𝑎
where 𝑛 = 1,2,3…
This means that the hamiltonian inside the box is exactly known. Besides, the only contribution to the
Hamiltonian will, at this stage, be assumed to be the kinetic energy and is therefore given by
1 𝑑2
̂=−
𝐻 3
2 𝑑𝑥 2
being the Schrödinger equation for the system

̂ 𝛹𝑛 𝑥 = 𝐸𝑛 𝛹𝑛 𝑥
𝐻 4
The energy that represents the exact energy of the 𝑛th level will be
̂ 𝛹𝑛
𝐻
𝐸𝑛 = 5
𝛹𝑛
The eigenfunctions of the Schrödinger equation form a complete set of orthonormal basis functions.
Therefore,
0 𝑖≠𝑗
< 𝛹𝑖 |𝛹𝑗 > = 𝛿𝑖𝑗 { 6
1 𝑖=𝑗
The Figure 2 shows the graphic representation of functions with their respective values and exact energies
of the states. We can observe that the number of nodes (place inside the box where the wave functions
dies) is equal to (𝑛-1) where 𝑖 is the quantum number of the state under study.
𝛹1 𝛹2 𝛹3
1.41421cos 3.14159𝑥 1.41421sin 6.28319𝑥 1.41421cos 9.42478𝑥

𝐸1 = 4.9348 𝐸2 = 19.7392 𝐸3 = 44.4132
Figure 2. The shapes of the first three exact eigenfunctions of the particle in a one-
dimensional box model by Mathematica.
2
Physical Chemistry
Thus, for example, the number of nodes in the function corresponding to the third state is equal to 2. The
energies presents in the Figure 2 correspond, in a.u., to the exact equation of the energy for a particle in a
one-dimensional box that is
𝜋 2 𝑛2
𝐸𝑛 = 7
2𝑎2
Now, we will verify the orthogonality by elemental integration techniques. However, orthogonality can be
easily established by studying graphical plots of the functions 𝛹𝑖 𝛹𝑗
The Figure 3 shows the shapes of the orthogonality basis functions
𝛹1 𝛹2 𝛹1 𝛹3 𝛹2 𝛹3
Figure 3. The shape of the functions 𝜳𝒊 𝜳𝒋 .
The most relevant we can see in the Figure 3 is that the shapes of the functions, in the graphic plots, are
symmetric and present the same areas dimension. The orthogonality of the functions is graphically
demonstrated.
These functions satisfy the < 𝛹𝑖 |𝛹𝑗 > = 𝛿𝑖𝑗 condition showed above in Eq. (6). Therefore, is
demonstrated, at the same time, that the overlap matrix is the unit matrix 𝕊 = 1.
If each of these functions is normalized, then set of functions 𝛹𝑖 is said to form a complete orthonormal
set. Any function that satisfies the boundary conditions of the system can be written as a linear
combination of this orthonormal basis set.
3
Physical Chemistry
2.1.2 Particle in a Two-Dimensional Box
For the two-dimensional system and following the Eqs. (3) and (4) the Schrödinger equation satisfies
ℏ2 𝜕 2 𝜕2
− ( 2 + 2 ) 𝛹𝑛 𝑥, 𝑦 = 𝐸𝑛 𝛹𝑛 𝑥, 𝑦 8
2𝑚 𝜕𝑥 𝜕𝑦
The position in the coordinates is −𝑎/2 ≤ 𝑥 ≤ 𝑎/2 and −𝑏/2 ≤ 𝑦 ≤ 𝑏/2 assumed a rectangular box in the
case that 𝑎 ≠ 𝑏 and a square box if 𝑎 = 𝑏.
𝑦
−𝑏/2
0,0 𝑥
𝑏/2
−𝑎/2 𝑎/2
Figure 4. Particle in a two-dimensional box −𝒂/𝟐 ≤ 𝒙 ≤ 𝒂/𝟐 and −𝒃/𝟐 ≤ 𝒚 ≤ 𝒃/𝟐.
Based on the Eq. (8) can be considered 𝐻 ̂𝑥 + 𝐻

̂𝑦 (independent operators). Thus, applying the same
methodology as in one-dimension, the functions used will be
2 𝑛𝑥 𝜋 𝑥 2 𝑛𝑥 𝜋 𝑥
𝛹𝑛𝑥 𝑥 = √ cos ( ) 𝛹𝑛𝑥 𝑥 = √ sin ( )
𝑎 𝑎 𝑎 𝑎
𝑛 = 𝑜𝑑𝑑 (9) 𝑛 = 𝑝𝑎𝑖𝑟 (10)
2 𝑛𝑦 𝜋 𝑦 2 𝑛𝑦 𝜋 𝑦
𝛹𝑛𝑦 𝑦 = √ cos ( ) 𝛹𝑛𝑦 𝑦 = √ sin ( )
𝑏 𝑏 𝑏 𝑏
So, a complete set of functions used will be
𝛹𝑛𝑥 𝑛𝑦 𝑥, 𝑦 = 𝛹𝑛𝑥 𝑥 𝛹𝑛𝑦 𝑦 11
and the energy
𝐸 = 𝐸𝑥 + 𝐸𝑦 12
The values of the exact energy, in a 2D box, are given by
𝜋 2 𝑛𝑥2 𝑛𝑦2
𝐸𝑛𝑥 𝑛𝑦 = + 13
2 𝑎2 𝑏2
4
Physical Chemistry
The Figure 5 represents the functions of three states, with the values of exact energies and symmetrical
functions (remember Eq. (11)), for a particle in a rectangular box (𝑎 ≠ 𝑏), that is to say, both dimensions of
the box must not be equal, to avoid degeneracies [3] as would happen in a square box.
𝛹11 𝛹12 𝛹22
1.82574cos 3.14159𝑥 cos 2,61799𝑦 1.82574cos 3.14159𝑥 sin 5.23599𝑦 1.82574sin 6.28319𝑥 sin 5.23599𝑦
𝐸11 = 8.36175 𝐸12 = 18,64260 𝐸22 = 33.44700
Figure 5. The shape of the three exact eigenfunctions for a particle in a rectangular box.
As we can see in Figure 5, for a 2D box, the nodes are represented by lines where state 12 has one node
and state 22 has two nodes.
Contrasting Figure 5 and 6 we can see, as 𝑎 ≠ 𝑏, the states 𝑛𝑥 = 1, 𝑛𝑦 = 2 and 𝑛𝑥 = 2, 𝑛𝑦 = 1 are not
degenerated. Thus, the absence of degeneracy is demonstrated for a rectangular box.
𝛹21
1.82574cos 2.61799𝑦 sin 6.28319𝑥

𝐸21 = 23.1662
Figure 6. The shape of the function 𝜳𝟐𝟏 and exact energy of the corresponding state. Respect to
𝜳𝟏𝟐 it can only observe difference in the position of the function.
5
Physical Chemistry
If the particle was in a square box (𝑎 = 𝑏) the states 𝛹12 and 𝛹21 will be degenerate (𝐸12 = 𝐸21 as Figure
7 shows
𝛹12 𝛹21
𝐸12 = 24,674 𝐸21 = 24,674

Figure 7. Shapes of functions 𝜳𝟏𝟐 and 𝜳𝟐𝟏 and degeneracy formed in states 12 and 21 in a
square box.
As we can observe, comparing Figure 5 with Figure 6, the energy of the state 12 and 21 do not seem
similar, meaning that there is not degeneracy [3]. So, we can conclude that, in a rectangular box, unless at
1
least two of the values 𝑎 or 𝑏 are integers, would has not degeneracy .
Figure 7 shows 𝛹12 and 𝛹21 functions represented in a square box, with the intention of seeing, clearly, the
difference between one and other states variating the box.
1
Accidental degeneracies are possible in a rectangular box (𝑎 ≠ 𝑏 . Sometimes, parameters of 2D box are not equal,
the “exact” energies of the levels could be to coincide.
6
Physical Chemistry
2.2 Particle in a Box with Potential
Now, we shall throughout 𝑉 ≠ 0 in the system. For an arbitrary potential, the Schrödinger equation has
not analytical solution (exact solution) and its must be solved by approximated methods such as linear
variation theory.
2.2.1 Linear Variations Method
A linear variation method [1] is a variation process which allows approximating to the exact solution of a
quantum system as a lineal combination of n linearly independent functions. The functions 𝜙 are real;
therefore, all coefficients 𝑐𝑖 and functions 𝛹𝑖 (which are called basis functions) are real. Due to
coefficients 𝑐𝑖 of expansion are unknown, the function 𝜙 is normalized. Thus, the variational integral is
̂ |𝜙𝑗 >
< 𝜙𝑖 |𝐻
𝜀= 14
< 𝜙𝑖 |𝜙𝑗 >
where
𝑛
𝜙 = 𝑐1 𝛹1° + 𝑐2 𝛹2° + ⋯ + 𝑐𝑛 𝛹𝑛° = ∑ 𝑐𝑖 𝛹𝑖° 15

𝑖=1
The coefficients 𝑐𝑖 are parameters to be determined by minimizing the variational integral, and the basis
functions 𝛹𝑖 must satisfy the boundary conditions of the problem. As a set of basis functions we will use
the exact functions of the particle in a box.
Then, through a little bit of algebra, we will get
ℍℂ = 𝜺𝕊ℂ 16
where ℍ is the matrix
̂ 𝛹𝑗° 𝑑𝜏
𝐻𝑖𝑗 = ∫ 𝛹𝑖° 𝐻 17
and
1
̂ = − 𝛻2 + 𝑉
𝐻 18
2
𝕊 is the overlap matrix
𝑆𝑖𝑗 = < 𝛹𝑖° |𝛹𝑗° > = 𝑆𝑗𝑖 19
Due to set of functions {𝛹𝑖° } is orthonormal, 𝑆𝑖𝑗 = 𝑆𝑖𝑗 and, therefore, Eq. (16) is reduced to
2
ℍℂ=𝜺ℂ 20
the matrix ℍ diagonalization, provides the coefficients of expansion (15) (eigenvectors) and the
approximate energies (eigenvalues).
2
As the functions are normalized, 𝕊 is the identity matrix (𝕊 = 1 .
7
Physical Chemistry
2.2.2 Nondegenerate Perturbation Theory
I shall now study perturbation theory [2] for a particle in a one-dimensional box and two-dimensional box.
The idea is to introduce an additional term to the exact Hamiltonian through a potential V. This term will be
assumed to be time-independent and is identified as the perturbation 𝐻 ̂ ′ . But, the perturbation treatments
of degenerate and nondegenerate energy levels differ.
̂ ° will be the hamiltonian operator of the unperturbed system and 𝛹𝑖° will be a complete set of
𝐻
̂°.
eigenfunctions of 𝐻
Nondegenerate perturbation theory let 𝛹𝑖° be the wave function of some particular unperturbed
nondegenerate level with energy 𝐸𝑖° .that appoints the complete set of eigenvalues and represents the
exact energy of the state’s levels. Therefore
̂ ° 𝛹𝑖° = 𝐸𝑖° 𝛹𝑖°

𝐻 21
so
̂ ° 𝛹𝑖°
𝐻
𝐸𝑖° = 22
𝛹𝑖°
The Hamiltonian of perturbed system is represented by
̂=𝐻
𝐻 ̂° + 𝐻
̂′ 23
̂ ′ is the perturbation, commented before, and the superscript ° denotes the unpertubed system.
where 𝐻
Due to aim is to get the relationship of the unknown eigenfunctions and eigenvalues of the perturbed
3
system with those known of the unpertubed system, it is introduced a parameter 𝜆 in the hamiltonian. This
parameter provides a gradually application, giving a continuous change from the unperturbed to the
perturbed system, so that
̂=𝐻
𝐻 ̂ ° + 𝜆𝐻
̂′ 24
where 𝛹𝑖 is the perturbed wave function into which 𝛹𝑖° will be become when the potential or perturbation is
applied. From Eqs. (4) and (23), the Schrödinger equation for 𝑖th perturbed state satisfying
̂ 𝛹𝑖 = (𝐻
𝐻 ̂ ° + 𝜆𝐻
̂ ′ )𝛹𝑖 = 𝐸𝑖 𝛹𝑖 25
It is important that 𝛹𝑖 satisfy
< 𝛹𝑖° |𝛹𝑖 >= 1 26
𝑘
Thus, all corrections 𝛹𝑖 meet the orthogonality condition with 𝛹𝑖°
𝑘
< 𝛹𝑖° |𝛹𝑖 > = δ0k 27
By a little bit of algebra, we will get the general term for 𝜆𝑛

𝑛−1
(𝐻 ̂ ′ 𝛹𝑖 𝑛−1 − ∑ 𝐸 𝑛−𝑘 𝛹𝑖 𝑘 = 0
̂ ° − 𝐸𝑖° )𝛹𝑖 𝑛 + 𝐻 28
𝑖
𝑘=0
3
When 𝜆 is zero the system is unpertubed. If 𝜆 grow up, the perturbation increase and 𝜆=1 the perturbation is fully
apply. As Eq. (25) depends on the parameter 𝜆, both the eigenfunction 𝛹𝑖 and the eigenvalue 𝐸𝑖 depend on 𝜆: 𝛹𝑖 =
𝛹𝑖 𝜆, 𝑞 and 𝐸𝑖 = 𝐸𝑖 𝜆 where 𝑞 = 𝑥, 𝑦, 𝑧 if is Cartesian coordinates system.
8
Physical Chemistry
The First-Order Energy Correction
𝑛
𝐸𝑖 is the 𝒏th-order correction to the energy. By the Eq. (28), for 𝑛 = 1, we have
° 1 ′
̂ − 𝐸𝑖 ) 𝛹
(𝐻
° ̂ 𝛹°𝑖 − 𝐸 1 𝛹°𝑖 = 0
+𝐻 29
𝑖 𝑖
multiplying by (𝛹𝑖° )* and integrating all space we have
1 ̂ ° − 𝐸𝑖° |𝛹𝑖 1 ̂ ′ |𝛹𝑖° >

𝐸𝑖 =< 𝛹𝑖° |𝐻 > +< 𝛹𝑖° |𝐻 30
Then
1 ̂ ′ |𝛹𝑖° >= ∫ 𝛹𝑖°∗ 𝐻

̂ ′ 𝛹𝑖° 𝑑𝜏
𝐸𝑖 = < 𝛹𝑖° |𝐻 31
4
Eq. (31) gives the first order energy correction. Thus, the energy for 𝑖th state will be
1
𝐸𝑖 ≈ 𝐸𝑖° + 𝐸𝑖 𝜆=1 32
The First-Order Wave-Function Correction
The 𝑘-order perturbation correction for the wave function can be expanding in terms of the complete,
̂ ° . For 𝑘=1:
orthonormal set of unperturbed eigenfunctions of the Hermitian operator 𝐻
1 1
𝛹𝑖 = ∑ 𝑐𝑘𝑖 𝛹𝑘° 33
𝑘
where
1
̂ ′ |𝛹𝑖° >
< 𝛹𝑘° |𝐻
𝑐𝑘𝑖 = 𝑘≠𝑖 34
𝐸𝑖° − 𝐸𝑘°
Setting 𝜆 = 1 and using just the first-order wave-function correction, we have as the approximation to the
perturbed wave function
1
̂𝑘𝑖
𝐻 ′
𝛹𝑖 = 𝛹𝑖° + 𝛹𝑖 = 𝛹𝑖° + ∑ 𝛹𝑘°
𝐸° − 𝐸𝑘° 35
𝑘≠𝑖 𝑖
being
̂𝑘𝑖
𝐻 ′ ̂ ′ |𝛹𝑖° > = ∫ 𝛹𝑘° 𝐻
=< 𝛹𝑘° |𝐻 ̂ ′ 𝛹𝑖° 𝑑𝜏 36
4
As < 𝛹𝑖° |𝛹𝑖° >= 1 and 𝐻 ̂ ° − 𝐸𝑖° |𝛹𝑖 1 >=< (𝐻
̂ ° − 𝐸𝑖° is hermitic, so < 𝛹𝑖° |𝐻 ̂ ° − 𝐸𝑖° )𝛹𝑖° |𝛹𝑖 1 >= 0. This result to Eq. (30)
gives Eq. (31).
9
Physical Chemistry
The Second-Order Energy Correction
As the first-order wave-function correction is already known, it is possible to calculate the second-order
1
energy correction. Through analogous procedure we used in 𝐸𝑖 , by Eq. (28), we can obtain the next
general term for the 𝑛-th correction of the energy of the 𝑖-th state
𝑛 ̂ ′ |𝛹 𝑛−1
𝐸𝑖 = < 𝛹𝑖° |𝐻 𝑖 > 37
2 ̂ ′ |𝛹 1 1
Thus, for the second energy correction, when 𝑛 = 2, we get 𝐸𝑖 =< 𝛹𝑖° |𝐻 𝑖 > and 𝛹𝑖 is the first
1 1 <𝛹𝑘° |𝐻
̂ ′ |𝛹𝑖° >
correction obtained before: 𝛹𝑖 = 𝑐𝑘𝑖 𝛹𝑘° = 𝛹𝑘° . Therefore, through a laborious process, we will
𝐸𝑖° −𝐸𝑘°
have
2
̂𝑘𝑖
|𝐻 ′ 2
|
𝐸𝑖 =∑ 38
𝐸𝑖° − 𝐸𝑘°
𝑘≠𝑖
2.3 Radiation/matter interaction
We are now ready to consider the time-dependent Schrödinger equation [5, 6]. If appropriate amounts of
energy are supplied to molecule, it would be possible to bring about transition between any two levels.
However, it is found experimentally that the atomic and molecular spectra contain far fewer lines than
predicted by the resonance condition, that is, 𝛥𝐸 = ℎ𝑣. This must mean that only certain transitions are
“allowed” or “preferred”.
Consider the transition between the 𝑚 and 𝑛 stationary states, † described by the state functions 𝛹𝑚 and
5
𝛹𝑛 . Since both 𝛹𝑚 and 𝛹𝑛 are solutions of time-dependent Schrödinger equation, it follows that their linear
combination 𝛹 must also be a solution of the same equation. We write
𝛹 = 𝑐𝑚 𝛹𝑚 𝑞, 𝑡 + 𝑐𝑛 𝛹𝑛 𝑞, 𝑡 39
where 𝑐𝑚 and 𝑐𝑛 are constants. Eq. (39), at the same time, must be rewritten as
𝛹 = 𝑐𝑚 𝑡 𝛹𝑚 𝑞, 𝑡 + 𝑐𝑛 𝑡 𝛹𝑛 𝑞, 𝑡 40
since transition can now occur between the 𝑚 and 𝑛 states. When the radiation field is applied, the initial
rate of transition is given by
𝑑𝑐𝑛 𝑡 𝑑𝑐𝑚 𝑡
= ∫ 𝛹𝑛∗ 𝑞, 𝑡 𝐽𝐶 ′ 𝛹𝑚 𝑞, 𝑡 𝑑𝑞 41
𝑑𝑡 𝑖ℏ
The hamiltonian 𝐽𝐶 ′ represents the electric field electric dipole moment interaction that is given by
𝐽𝐶 ′ = 𝜺 · 𝝁 42
where 𝜇𝑛𝑚 , the transition dipole moment, is given by
𝜇𝑛𝑚 = ∫ 𝛹𝑛∗ 𝑥 𝜇𝛹𝑚 𝑥 𝑑𝑥 43
5
By stationary state it is meant that the state remains unchanged in the absence of external perturbations.
10
Physical Chemistry
3. Results
Having done all procedure of mathematical model on concepts explained above, developed by means of
Mathematica and COMSOL, the results obtained will be shown applying atomic units (u.a.) for all quantum.
Potentials Applied
Now, if the particle of the system is subjected to a potential, we will be able to observe some variations.
It will be use two types of potential from which we will observe changes in the system and whose
approximations to the lowest ground state and some excited states will be carried out through linear
variations method and the perturbation theory:
Asymmetric potential Symmetric potential

1D 𝑐1 ℯ −𝑐2𝑥 𝑅 − √𝑅 2 − 𝑥 2
𝑥+𝑐 2 +𝑦
2D 𝐷1 ℯ −𝐷2 𝑅 − √𝑅2 − 𝑥 2 ∀𝑦
Table 1. Types of potential applied where 𝑹 = 𝑽𝟎 ^𝟐 + 𝒂^𝟐⁄𝟒 ⁄ 𝟐 ∗ 𝑽𝟎 .
The shape of the asymmetric potentials is:
∞ ∞
Figure 8. The shape of the asymmetric potential 𝑽 𝒙 = 𝟒. 𝟓𝓮−𝟓.𝟓𝒙 in a one-dimensional box.
𝟐
Figure 9. The shape of the asymmetric potential 𝑽 𝒙, 𝒚 = 𝟒. 𝟏𝟓 ∗ 𝓮−𝟐.𝟓∗ 𝒙+𝟎.𝟐 +𝒚 in a two-dimensional box.
11
Physical Chemistry
where the potential applied is an exponential potential, for example, 𝑐1 ℯ −𝑐2𝑥 . The shape of the potential in
the graphic plot, shows, clearly, that the potential is a falling exponential curve −𝑥 and, for this reason,
completely asymmetric.
The shape of the symmetric potentials is:
∞ ∞
Figure 10. The shape of the symmetric potential 𝑽 𝒙 = 𝑹 − √𝑹𝟐 − 𝒙𝟐 in a one-dimensional box.
Figure 11. The shape of the symmetric potential 𝑽 𝒙, 𝒚 = 𝑹 − √𝑹𝟐 − 𝒙𝟐 ∀𝒚 in a two-dimensional box.
From graphic plots represented above, we can already observe the clear difference in respect of the
symmetry of both potentials.
12
Physical Chemistry
3.1 Approximation by Linear Variation Method
Now, asymmetric and symmetric potential is applied on a particle in a one and two-dimensional box,
providing some changes in the system that will be treated to make the corresponding approximations.
Firstly, the approximations will be realized by linear variation method chosen 12 basis functions.
3.1.1 Particle in a 1D System with 𝑽 ≠ 𝟎 inside the Box
A big exponential and symmetric potential were applied . So, the variational functions obtained and the
probability densities are showed by Figure 12
Figure 12. The shape of the first three 𝜳𝒊 and |𝜳𝒊 |𝟐 with the asymmetric potential 𝑽 𝒙 = 𝟒. 𝟓𝓮−𝟓.𝟓𝒙 applied in a
one-dimensional box.
Figure 13. The shape of the first three 𝜳𝒊 and |𝜳𝒊 |𝟐 with the symmetric potential 𝑽 𝒙 = 𝟎. 𝟓 − √𝟎. 𝟐𝟓 − 𝒙𝟐 applied
in a one-dimensional box.
Through the Figure 12 and 13, we can observe different effects in the functions, depending on the
potential applied. In Figure 12 it is shown the tendency of the functions is go places to the right as
consequence of the asymmetric potential applied. However, in Figure 13 the functions do not experiment
any distortion due to the symmetric potential distributes the charge density as equal form in both parts of
the box.
It should be noted that if the asymmetric potential is small, we would not have a clear vision of the
distorted functions by plots, because the effect of the potential in the functions is minimal. Now, we will do
a numerical comparative through the values of the approximation energies obtained after the potentials.
Thus, the energies of the system are:
13
Physical Chemistry
𝒔.𝒂𝒔𝒚𝒎. 𝒃.𝒂𝒔𝒚𝒎. 𝒔𝒚𝒎.

𝑺𝒕𝒂𝒕𝒆 𝒊 𝑬𝒊 𝑬𝒊 𝑬𝒊
𝟏 5.08028 10.1026 4.96578
𝟐 19.9168 29.4086 19.80780
𝟑 44.5983 56.1776 44.49080
𝟒 79.1446 91.4510 79.03790
𝒔.𝒂𝒔𝒚𝒎.
Table 2. The energy values for the first four states provided by 𝑬𝒊 corresponding to a small asymmetric potential
𝒃.𝒂𝒔𝒚𝒎. 𝒔𝒚𝒎.
𝑽 𝒙 = 𝟎. 𝟏𝟐𝓮−𝟑.𝟓𝒙 , 𝑬𝒊 corresponding to a big asymmetric potential 𝑽 𝒙 = 𝟒. 𝟓𝓮−𝟓.𝟓𝒙 and 𝑬𝒊
corresponding to a symmetric potential 𝑽 𝒙 = 𝟎. 𝟓 − √𝟎. 𝟐𝟓 − 𝒙𝟐 .
6
As well as the verification of the asymmetric or symmetric distribution of charge density [4] in the
momentum space of the variational functions is showed by Table 3

𝝆𝒊 𝝆𝒊 𝝆𝒊
𝑺𝒕𝒂𝒕𝒆 𝒊 −𝒂/𝟐 ≤ 𝒙 ≤ 𝟎 𝟎 < 𝒙 ≤ 𝒂/𝟐 −𝒂/𝟐 ≤ 𝒙 ≤ 𝟎 𝟎 < 𝒙 ≤ 𝒂/𝟐 −𝒂/𝟐 ≤ 𝒙 ≤ 𝟎 𝟎 < 𝒙 ≤ 𝒂/𝟐
𝟏 0.495039 0.504961 0.265678 0.734322 0.5 0.5
𝟐 0.502920 0.497080 0.579364 0.420636 0.5 0.5
𝟑 0.499902 0.500098 0.490089 0.509911 0.5 0.5
𝟒 0.50082 0.499180 0.554533 0.445467 0.5 0.5
Table 3. Charge density distribution of variational functions in a 1D box with the same potentials applied above where
the simplifications in superscript of 𝝆𝒊 have the same meaning as in Table 2.
From the most part of the box subject to a potential charge to the least subject to this potential (since the
shape of the potential in Figure 8 implies such a distribution). In this case, logically, the charge density is
displaced to the right of the box, as we can observe by the graphic plot in Figure 12. This numeric
difference in the Table 3, provides a clear idea about the distorted or displacement that the perturbed
functions experience subject to a perturbation.
Judging Table 3, if we compare the distributions of charge density in small asymmetric potential case we
can observe that the effect in the functions is almost symmetric. However, in the big asymmetric potential
case and observing state 1, for example, we have already a clear vision of the charge density distribution
to the right which confirms the asymmetric distribution of the functions. For another part, in the symmetric
potential case the values of the charge density confirm that the function do not experiment any distortion
as we have already commented above.
6
Determining the probability distribution for the particle in state 𝛹𝑖 . As just the probability density to find the particle
located within the infinitesimal range: 𝜌𝑖 = |𝛹𝑖 |2.
14
Physical Chemistry
3.1.2 Particle in a 2D System with 𝑽 ≠ 𝟎 inside the Box
The functions obtained and the corresponding density probabilities for a symmetric and asymmetric
potential applied in a rectangular box (𝑎 = 1, 𝑏 = 1.2), to avoid degeneracies, are:
𝛹4 |𝛹4 |2
𝛹3
|𝛹3 |2
𝛹2 |𝛹2 |2
𝛹1
|𝛹1 |2
𝟐
Figure 14. The shapes of the first four 𝜳𝒊 and |𝜳𝒊 |𝟐 with the asymmetric potential 𝑽 𝒙, 𝒚 = 𝟒. 𝟏𝟓 ∗ 𝓮−𝟐.𝟓∗ 𝒙+𝟎.𝟐 +𝒚 applied in a two-
dimensional box.
Other shapes to obtain a clear vision of distorted functions in a two-dimensional box as consequence of
asymmetric potential applied are showed in Figure 15
𝛹1 𝛹2 𝛹3 𝛹4
° °
𝛹11 𝛹11 °
𝛹11 °
𝛹11
𝟐
Figure 15. The contour plot of the first four 𝜳𝒊 with the asymmetric potential 𝑽 𝒙, 𝒚 = 𝟒. 𝟏𝟓 ∗ 𝓮−𝟐.𝟓∗ 𝒙+𝟎.𝟐 +𝒚 applied in a two-
dimensional box.
15
Physical Chemistry
Applying the symmetric potential, the shape of functions obtained were:
𝛹4 |𝛹4 |2
𝛹3 |𝛹3 |2
°
𝛹11
|𝛹2 |2
𝛹2
°
𝛹11
° 2
𝛹1 𝛹111
|𝛹 |
Figure 16. The shapes of the first four 𝜳𝒊 and |𝜳𝒊 |𝟐 with the asymmetric potential 𝑽 𝒙, 𝒚 = 𝟎. 𝟓 − √𝟎. 𝟐𝟓 − 𝒙𝟐 ∀𝒚 .
applied in a two-dimensional box.
° °
𝛹11 𝛹11
Analyzing the variations in the energies of the different energetic levels of the two-dimensional system by
Table 4

𝑺𝒕𝒂𝒕𝒆 𝒊 𝑬𝒊 𝑬𝒊 𝑬𝒊
𝟏 8.50847 12.0119 8.39785
𝟐 18.8138 23.3302 18.6787
𝟑 23.3024 26.635 23.2469
𝟒 33.9543 37.827 33.5277
𝒔.𝒂𝒔𝒚𝒎.
Table 4. The energy values for the first four states provided by 𝑬𝒊 corresponding to a small asymmetric potential
𝟐 𝒃.𝒂𝒔𝒚𝒎.
𝑽 𝒙, 𝒚 = 𝟎. 𝟏𝟓𝓮−𝟐.𝟓 𝒙+𝟎.𝟐 +𝒚 , 𝑬𝒊 corresponding to a big asymmetric potential 𝑽 𝒙, 𝒚 = 𝟒. 𝟏𝟓 ∗
𝟐 𝒔𝒚𝒎.
𝓮−𝟐.𝟓∗ 𝒙+𝟎.𝟐 +𝒚 and 𝑬𝒊 corresponding to a symmetric potential 𝑽 𝒙, 𝒚 = 𝟎. 𝟓 − √𝟎. 𝟐𝟓 − 𝒙𝟐 ∀𝒚 .
And the values of charge density

𝟏 0.493674 0.506326 0.3499070 0.650093 0.5 0.5
𝟐 0.503698 0.496302 0.5760040 0.423996 0.5 0.5
𝟑 0.494124 0.505876 0.356809 0.643191 0.5 0.5
𝟒 0.503433 0.496567 0.573510 0.426569 0.5 0.5
Table 5. Charge density distribution of variational functions in a 2D box with the potentials used in Table 4.
16
Physical Chemistry
Through the results showed in Table 4 we can observe the great effect that big asymmetric potential
exercises on functions and energies providing energy values very little approximated to the “exact”
energies . However, the effect of the small asymmetric potential is less than the big potential due to the
energies are more similar to the “exact” energies of the system. But, realizing the comparative between
three potentials, we can say that the most approximated is when symmetric potential is applied, the same
for a particle in a one dimensional box..
Table 5 shows the verification of the asymmetric and symmetric charge density distribution of the functions
depending of the potential applied. For a small asymmetric potential the probabilities are practically similar
in both parts of the box and symmetric potential case the probabilities are equal in two parts. The most
clear difference resides in big asymmetric potential where the distribution, numerically and visually, it is
demonstrated the distortion to the right of the box as consequence of the asymmetry.
3.2 Approximation by Perturbation Theory Time-Independent
In this section, the particle will be evaluated by perturbation theory time-independent, where the
perturbation 𝐻̂ ′ is chosen to be the same potentials applied for a particle studied by linear variation
method. We will have a certain number of perturbed states for which other certain number of states will be
used to calculate the perturbation. In this case, the number of perturbed states will be 4 and the number of
states to calculate this perturbation will be 20.
3.2.1 Particle in a 1D System with Perturbation inside the Box
̂ ′ the energies and

Now, chosen a big and small asymmetric and symmetric potential as perturbation 𝐻
probabilities density are:
𝟏 𝟐
𝒊 𝑬°𝒊 𝑬𝒊 𝑬𝒊 𝑬𝒕𝒐𝒕
𝟏 4.9348 0.146030 -0.0005511590 5.08028
𝟐 19.7392 0.177568 0.0000624632 19.9168
𝟑 44.4132 0.184966 0.0000934723 44.5983
𝟒 78.9568 0.187702 0.0000707229 79.1446
𝟏
Table 6. Values of the Exact Energy of the Unperturbed Box 𝑬°𝒏 , the First Order Perturbation Energy 𝑬𝒏 , the Second
𝟐
Order Perturbation Energy 𝑬𝒏 and the Total Energy 𝑬𝒕𝒐𝒕 for the 𝒊th Level of the Particle in a 1D Box with 𝑽 𝒙 =
𝟎. 𝟏𝟐𝓮−𝟑.𝟓𝒙 .
𝟏 𝟐
𝟏 4.9348 7.21657 -3.15484 8.99654
𝟐 19.7392 10.6971 -0.421295 30.0150
𝟑 44.4132 11.7462 0.389597 56.5490
𝟒 78.9568 12.1637 0.446217 91.5667
𝟏
𝟐
𝟒. 𝟓𝓮−𝟓.𝟓𝒙 .
17
Physical Chemistry
𝟏 𝟐
𝟏 4.9348 0.0361471 0.0000517133 4.9709
𝟐 19.7392 0.0807531 -0.0000558346 19.8199
-7
𝟑 44.4132 0.0925738 2.31083×10 44.5058
-6
𝟒 78.9568 0.0976427 9.74261×10 79.0545
𝟏
𝟐
𝟎. 𝟓 − √𝟎. 𝟐𝟓 − 𝒙𝟐 .

𝟏 0.495025 0.504975 0.216085 0.783915 0.5 0.5
𝟐 0.502941 0.497059 0.675636 0.324364 0.5 0.5
𝟑 0.499906 0.500094 0.527671 0.472329 0.5 0.5
𝟒 0.500823 0.499177 0.579755 0.420245 0.5 0.5
Table 9. Charge density distribution of perturbed functions in a 1D box with the same potentials used in Table 2.
Comparing Table 2 and 6 we can observe the same energy approximation for a small asymmetric
potential. But, when the potential is big, though was the same potential applied in linear variation method,
the energy are not the same. This fact demonstrate that the linear variation method and perturbation
theory do not exercise the same effect in the system for a big asymmetric potentials. In the symmetric
potential case, as it is not very big, the perturbed method provides good results (synchronized with linear
variation method).
By Table 9, perturbed functions, as consequence of the potential applied, undergo a displacement to the
right for an asymmetric case. The reason that the perturbed functions are distorted to the right is due to the
fact that exponential potential decreases with 𝑥.
3.2.2 Particle in a 2D System with Perturbation inside the Box
Applying nondegenerate perturbation theory time-independent for a rectangular box, the energies and
probabilities density were:
𝟏 𝟐
𝟏 8.36175 0.147369 -0.000645558 8.50847
𝟐 18.6426 0.171208 0.0000223647 18.8138
𝟑 23.1662 0.176495 0.0005036600 23.3024
𝟒 33.447 0.136717 -0.0004683430 33.6059
𝟏
𝟐
Order Perturbation Energy 𝑬𝒏 and the Total Energy 𝑬𝒕𝒐𝒕 for the 𝒊th Level of the Particle in a 2D Box with 𝑽 𝒙, 𝒚 =
𝒙+𝟎.𝟐 𝟐 +𝒚
𝟎. 𝟏𝟓 ∗ 𝓮−𝟐.𝟓∗ .
18
Physical Chemistry
𝟏 𝟐
𝟏 8.36175 4.77210 -0.4941390 11.9448
𝟐 18.6426 4.73674 0.0171189 23.3964
𝟑 23.1662 4.88302 0.3855240 26.5902
𝟒 33.447 3.78249 -0.358490 37.8642
𝟏
𝟐
Order Perturbation Energy 𝑬𝒏 and the Total Energy 𝑬𝒕𝒐𝒕 for the 𝑖th Level of the Particle in a 2D Box with 𝑽 𝒙, 𝒚 =
𝒙+𝟎.𝟐 𝟐 +𝒚
𝟒. 𝟏𝟓 ∗ 𝓮−𝟐.𝟓∗ .
𝟏 𝟐
𝟏 8.36175 0.0361471 -0.0000503996 8.39784
𝟐 18.6426 0.0361471 -0.0000503996 18.6787
𝟑 23.1662 0.0361471 -0.0000503996 23.2469
𝟒 33.447 0.0807532 0 33.5277
𝟏
𝟐
Order Perturbation Energy 𝑬𝒏 and the Total Energy 𝑬𝒕𝒐𝒕 for the 𝒊th Level of the Particle in a 2D Box with 𝑽 𝒙, 𝒚 =
𝟎. 𝟓 − √𝟎. 𝟐𝟓 − 𝒙𝟐 ∀𝒚 .

𝟏 0.493650 0.506350 0.334844 0.665156 0.5 0.5
𝟐 0.503734 0.496266 0.599735 0.400265 0.5 0.5
𝟑 0.502624 0.497376 0.568570 0.431430 0.5 0.5
𝟒 0.494112 0.505888 0.348837 0.651163 0.5 0.5
Table 13. Verification of the asymmetric and symmetric distributions of the charge density of the first four perturbed
states. The superscripts in 𝝆 refer to the same potentials 𝑽 𝒙, 𝒚 used in Table 4.
As we can observe, in Tables 10, 11 and 12, the order is aleatory due to the perturbed functions are
dispersed in the all range.
Using perturbed theory and by Table 12 we have demonstrated that the corrections are, practically, equals
between them and, the energies approximated are the same for both method applied except in big
asymmetric potential case where the first order correction of energy is very high which thing does not
make any sense.
19
Physical Chemistry
3.3 Selection Rules of Transitions
Now, we are going to study the possible transitions of a system from one quantum state to another. So, for
the “exact” model of particle in a one-dimensional box the values of the integral are:
𝒏→𝒎 |𝝁𝒏𝒎 | 𝝁𝒏𝒎 𝟐 / 𝝁𝟏,𝟐 𝟐
1→2 0.377256 1
1→3 0 0
1→4 0.0301805 0.0064
1→5 0 0
1→6 0.00831503 0.000485798
𝟐𝝅 𝟐𝝅 𝟐𝝅
Table 14. The values of the | < 𝜳∗𝒏 𝒙𝜳𝒎 > | and ( < 𝜳∗𝒏 𝒙𝜳𝒎 > 𝟐 / < 𝜳∗𝟏 𝒙𝜳𝟐 > 𝟐 when the transition go
𝟑 𝟑 𝟑
from 𝒏 = 𝟏 to 𝒎 = 𝟐, 𝟑, 𝟒, 𝟓, 𝟔.
As we can observe the integral is zero if the function 𝛹𝑛∗ 𝑥 𝑥𝛹𝑚 𝑥 is odd and nonzero if the function is
even. When 𝛹𝑛 𝑥 and 𝛹𝑚 𝑥 have the same parity, dipole radiation cannot occur, in which case, we are in
a forbidden transition. This provides the selection rules where the parity of the state must be change so
there is electric dipole radiation. Table 14 shows that the biggest 𝜇𝑛𝑚 value is for transition 1 → 2 due to
from fundamental state to excited state we have the greatest energy transition. This is the reason to do a
division of the transition dipole moment between of 1 → 2 transition’s dipole moment.
So, the selection rules establish the useful results:
𝛹𝑜𝑑𝑑 → 𝛹𝑒𝑣𝑒𝑛 𝑎𝑙𝑙𝑜𝑤𝑒𝑑
𝛹𝑜𝑑𝑑 → 𝛹𝑜𝑑𝑑 𝑓𝑜𝑟𝑏𝑖𝑑𝑑𝑒𝑛
20
Physical Chemistry
3.4 Comparative Results between approximated Methods and COMSOL
With the intention to compare the approximate results obtained by linear variation method and perturbation
theory, we require a pattern with which compare. For this reason we have used a numerical integration
method based on the finite elements theory. This method is implemented in the COMSOL, and as we can
use an excellent discretization, due to the small dimensionality of the problem, it makes these calculations
provide quasi-exact results. Thus, the energies obtained in a 1D and 2D box, applying big and small
asymmetric potential, through COMSOL were:
𝑺𝒕𝒂𝒕𝒆 𝑬 𝑳𝒊𝒏𝒆𝒂𝒓 𝑽𝒂𝒓𝒊𝒂𝒕𝒊𝒐𝒏 𝑴. 𝑬 𝑷𝒆𝒓𝒕𝒖𝒓𝒃𝒂𝒕𝒊𝒐𝒏 𝑻. 𝑪𝑶𝑴𝑺𝑶𝑳

1 10.1026 8.99654 10.102552
2 29.4086 30.015 29.408563
3 56.1776 56.549 56.177549
4 91.451 91.5667 91.450811
5 136.085 136.112 136.084322
Table 15. The energy values of particle in a One-dimensional box by Linear Variation Method, Nondegenerate
Perturbation Theory and COMSOL using 𝑽 𝒙 = 𝟒. 𝟓𝓮−𝟓.𝟓𝒙 .

1 5.08028 5.08028 5.080283
2 19.9168 19.9168 19.916837
3 44.5983 44.5983 44.598279
4 79.1446 79.1446 79.144608
5 123.559 123.559 123.559103
Table 16. The energy values of particle in a One-dimensional box by Linear Variation Method, Nondegenerate
Perturbation Theory and COMSOL using 𝑽 𝒙 = 𝟎. 𝟏𝟐𝓮−𝟑.𝟓𝒙 .

1 12.0119 11.9448 12.011446
2 23.3302 23.3964 23.323711
3 26.6350 26.5902 26.632627
4 37.8270 37.8642 37.815004
5 41.0245 41.0459 40.7339
Table 17. The energy values of particle in a Two-dimensional box by Linear Variation Method, Nondegenerate
𝟐
Perturbation Theory and COMSOL using 𝑽 𝒙, 𝒚 = 𝟒. 𝟏𝟓 ∗ 𝓮−𝟐.𝟓∗ 𝒙+𝟎.𝟐 +𝒚 .

1 8.50847 8.50847 8.508472
2 18.8138 18.8138 18.813789
3 23.3024 23.3024 23.3024
4 33.6059 33.6059 33.605828
5 35.9543 35.9543 35.953937
Table 18. The energy values of particle in a Two-dimensional box by Linear Variation Method, Nondegenerate
𝟐
Perturbation Theory and COMSOL using 𝑽 𝒙, 𝒚 = 𝟎. 𝟏𝟓 ∗ 𝓮−𝟐.𝟓∗ 𝒙+𝟎.𝟐 +𝒚 .
21
Physical Chemistry
As we can observe COMSOL provides quasi-successful results with a wider range of decimals. Between
results obtained by linear variation method and perturbation theory the most approximated to the
COMSOL’s energies are those provided by linear variation method. This indicates that linear variation
method works very well for a big potentials and perturbation theory is not a good method because it works
bad in a systems subject to a big potential, except in cases of small asymmetric potential where both
methods actuate from the same way due to the perturbation theory works well for a systems subject to
perturbations which involve small potentials and changes.
22
Physical Chemistry
4. Discussion
The Schrödinger equation for real systems becomes difficult to handle, and analytical solutions are only
available for very simple systems, which we described as fundamental systems in this module. Numerical
approaches can deal with more complex problems and are necessary to deal with real systems.
Using linear combination of solutions of the fundamental systems to build something similar to the real
system. Strictly speaking, linear combinations must be solutions of the same differential equation to
provide an accurate result. Thus, applying the two mathematical techniques, perturbation and variation
theory, that provided a good approximation along with an estimate of their accuracy, we have observed,
through the results obtained, that both approximation method for an equal potentials provides similarly
results about the energies approximated.
Comparing two methods we have verified that for a small asymmetric or symmetric potential the difference
in the effect the differences exerted by one and the other is insignificant. However, when we apply a big
asymmetric potential we can observe a much more evident difference between the energies where
perturbation theory seems to be a more optimal method than linear variations for providing an energy more
approximate to the "exact" one but this is due to that the perturbation theory is not a variational method
and in the face of a very big perturbation it can give energies both above and below the “exact” one
generating an seism. Therefore, we can conclude by saying that linear variation method is a better
mathematical technique for the approximation to “exact” model than perturbation theory time-independent
due to linear variation method is better for combining system of comparable weighting and the modification
is applied, directly, in the wave function. Nevertheless, perturbation theory is for small changes to a known
system where the Hamiltonian is modified, that is to say, perturbation theory works well when the
perturbation 𝐻 ̂ ′ is smaller than 𝐻
̂ ° . Is for this reason that when we applied a big potential, though was the
same, the result about the energies are different. Despite, the latter is the best for that.
In addition to this, we also did a comparative between the both method with a more exact numerical
method implemented in COMSOL package. Where it is observed that the numerical method applied by
COMSOL provided a greater and better approximation of the energies due to it allows doing a
discretization stage. This discretization involucres new approximation to the resolution of the numerical
process by finite elements method that allows realizing an analysis much more precise of the system.
Regarding the electronic transitions, we also demonstrate the selection rules in the parity transitions.
Where from fundamental state to the first excited state it is obtained the great value of transition
momentum, that is to say, it is the highest intensity transition.
In conclusion, we can say that quantum chemistry covers abstract and complex concepts which are very
difficult to understand. That is the reason why it is convenient to apply the sentence by a great thinker:
“I hear and I forget, I see and I remember, I do and I understand” – Confucius
23
Physical Chemistry
5. Annexes
1. Nondegenerate perturbation theory time-independent for an asymmetric potential applied in a

2. Linear variation method for an asymmetric potential applied in a one-dimensional box.
3. Nondegenerate perturbation theory time-independent for a symmetric potential applied in a

4. Linear variation method for a symmetric potential applied in a one-dimensional box.
5. Selection Rules of Transitions.
6. Impr. Pant. of COMSOL for a big potential applied in a one-dimensional box and rectangular
box.
9. Nondegenerate perturbation theory time-independent for an asymmetric potential applied in a

two-dimensional box.
11. Linear variation method for an asymmetric potential applied in a two-dimensional box.
13. Nondegenerate perturbation theory time-independent for a symmetric potential applied in a

two-dimensional box.
14. Linear variation method for a symmetric potential applied in a two-dimensional box.
25
H* 1. Nondegenerate Perturbation Theory Time-Independent applied
for a Big Asymmetric Potential applied in a One-dimensional Box *L
ClearAll@"Global`*"D;
H* The length of the box *L

a = 1.0;
H* 'ne' is nth-state perturbed and 'lon' is the number

of states used to calculate the perturbation of each state *L
ne = 5;
lon = 20;
H* Big potential *L
pot@x_D := 4.5 * [email protected] * x aD;
H* Small potential *L
H* pot@x_D:=0.12*[email protected]*xaD; *L
H* Introducing the general equations of the system *L

fx@nx_D :=
If@OddQ@nxD True, Sqrt@2 aD * Cos@nx * Pi * x aD, Sqrt@2 aD * Sin@nx * Pi * x aDD;
ham@fi_D := -H1 2.0L * D@fi, 8x, 2<D;
E0@ii_D := ham@fx@iiDD fx@iiD Chop;
E1@ii_D := NIntegrate@fx@iiD * pot@xD * fx@iiD, 8x, -a 2, a 2<D Chop;
H* The first and second energies corrections *L

For@i = 1, i £ ne, i ++,
E2@iD = 0;
For@j = 1, j £ lon, j ++,
If@E0@jD ¹ E0@iD,
as = NIntegrate@fx@jD * pot@xD * fx@iD, 8x, -a 2, a 2<D Chop;
as1 = E0@iD - E0@jD;
E2@iD = E2@iD + as ^ 2 as1D;
D;
Print@"nx=", i, " E0@", i, "D=", E0@iD, " E1@", i, "D = ",
E1@iD, " E2@", i, "D=", E2@iD, " E@", i, "D=", E1@iD + E2@iD + E0@iDD
D;
nx=1 E0@1D=4.9348 E1@1D = 7.21657 E2@1D=-3.15484 E@1D=8.99654
nx=2 E0@2D=19.7392 E1@2D = 10.6971 E2@2D=-0.421295 E@2D=30.015
nx=3 E0@3D=44.4132 E1@3D = 11.7462 E2@3D=0.389597 E@3D=56.549
nx=4 E0@4D=78.9568 E1@4D = 12.1637 E2@4D=0.446217 E@4D=91.5667
nx=5 E0@5D=123.37 E1@5D = 12.3672 E2@5D=0.37511 E@5D=136.112

2 Box1D_Perturb_Pot_NO_Symmetric.nb
H* Obtaining the First-Order Wave-Functions Corrections *L

hij@i_, j_D := NIntegrate@fx@iD * pot@xD * fx@jD, 8x, -a 2, a 2<D Chop;
c@kk_, ii_D := hij@kk, iiD HE0@kkD - E0@iiDL;
For@k = 1, k £ ne, k ++,
li = k - 1; ls = k + 1;
fk = fx@kD + Sum@c@k, iD * fx@iD, 8i, 1, li<D + Sum@c@k, iD * fx@iD, 8i, ls, lon<D;
cte = 1 NIntegrate@fk ^ 2, 8x, -a 2, 0, a 2<D;
fun@kD = Sqrt@cteD * fk Expand Chop;
D;
H* Verifying non orthogonality of the perturbed functions *L

solap = Table@0, 8i, ne<, 8j, ne<D;
For@i = 1, i £ ne, i ++,
For@j = i, j £ ne, j ++,
solap@@i, jDD = NIntegrate@fun@iD * fun@jD, 8x, -a 2, 0, a 2<, AccuracyGoal ® 8D Chop;
If@j ¹ i, solap@@j, iDD = solap@@i, jDDD;
D;
D;
MatrixForm@solapD
1. -0.0254106 0.116032 -0.0465786 -0.0180353
-0.0254106 1. 0.0479004 0.0581195 0.0262925
0.116032 0.0479004 1. -0.036533 0.0358754
-0.0465786 0.0581195 -0.036533 1. 0.025688
-0.0180353 0.0262925 0.0358754 0.025688 1.
H* Veryfing the asymmetric distributions

of charge density in the perturbed functions *L
For@i = 1, i £ ne, i ++,
Print@"For fun@", i, "D: Ρ between -a2 and 0 = ", NIntegrate@fun@iD ^ 2, 8x, -a 2, 0<D,
" and Ρ between 0 and a2 = ", NIntegrate@fun@iD ^ 2, 8x, 0, a 2<DD;
D;
H* The shape of the probabilities of the perturbed functions *L

Plot@8pot@xD * 0.05, fun@1D ^ 2, fun@2D ^ 2, fun@3D ^ 2<, 8x, -a 2, a 2<,
PlotRange ® All, PlotStyle ® [email protected], Axes ® 8True, False<,
AxesStyle ® Directive@Black, [email protected], GridLines ® 88-a 2, a 2<, 8<<,
GridLinesStyle ® Directive@Black, [email protected], Filling -> Axis, AspectRatio ® 0.5D
Box1D_Perturb_Pot_NO_Symmetric.nb 3
For fun@1D: Ρ between -a2 and 0 = 0.216085 and Ρ between 0 and a2 = 0.783915
-0.4 -0.2 0.0 0.2 0.4
H* The shape of the perturbed functions with big asymmetric potential applied *L
Plot@8pot@xD * 0.05, fun@1D, fun@2D, fun@3D<, 8x, -a 2, a 2<,

-0.4 -0.2 0.0 0.2 0.4

H* 2. Linear Variation Method for
an Asymmetric Potential applied in a One-dimensional Box *L
H* Introducing dates and wavefunction equation *L

nf = 12;
a = 1.0;
fi@nx_D :=
H* Defining the big asymmetric potential applied *L

pot@x_D := 4.5 * [email protected] * x aD;
H* Defining the big asymmetric potential applied *L
H* pot@x_D:=0.12*[email protected]*xaD; *L
H* Defining the hamiltonian operator *L

ham@fi_D := H-1 2.0L * D@fi, 8x, 2<D + pot@xD * fi;
H* Building the matrix *L

mat = Table@0, 8i, nf<, 8j, nf<D;
For@i = 1, i £ nf, i ++,
For@j = i, j £ nf, j ++,
mat@@i, jDD = NIntegrate@fi@iD * ham@fi@jDD, 8x, -a 2, 0, a 2<, AccuracyGoal ® 10D;
If@j ¹ i, mat@@j, iDD = mat@@i, jDDD;
D;
D;
H* Matrix diagonalization *L
ene = Eigenvalues@matD Chop;
vec = Eigenvectors@matD Chop;
H* Ordering of energies an vectors from lowest to highest *L

For@i = 1, i £ nf - 1, i ++,
For@j = i + 1, j £ nf, j ++,
ei = ene@@iDD; ej = ene@@jDD;
veci = vec@@iDD; vecj = vec@@jDD;
If@ej < ei, ene@@iDD = ej; ene@@jDD = ei; vec@@iDD = vecj; vec@@jDD = veciD;
D;
D;
H* Graphic plot of big asymmetric potential applied *L

Plot@pot@xD, 8x, -a 2, a 2<, PlotRange ® All,
PlotStyle ® [email protected], Axes ® 8True, False<,
ene
2 Box1D_Variational_Pot_NO_Symmetric.nb
-0.4 -0.2 0.0 0.2 0.4
810.1026, 29.4086, 56.1776, 91.451, 136.085,

190.43, 254.598, 328.622, 412.516, 506.293, 610.021, 724.353<
H* Building a column vector with basis functions *L

fbasis = Table@0, 8i, nf<D;
For@i = 1, i £ nf, i ++,
fbasis@@iDD = fi@iD;
D;
H* Obtaining the variational functions *L funV = vec.fbasis;
Plot@8funV@@1DD, funV@@2DD, funV@@3DD, pot@xD * 0.05<, 8x, -a 2, a 2<,

-0.4 -0.2 0.0 0.2 0.4
H* Verify the asymmetric distribution of charge density of the

variational functions as consequence big asymmetric potential applied *L
For@i = 1, i £ 6, i ++,
Print@"For funV@", i,
"D: Ρ between -a2 and 0 = ", NIntegrate@funV@@iDD ^ 2, 8x, -a 2, 0<D,
" and Ρ between 0 and a2 = ", NIntegrate@funV@@iDD ^ 2, 8x, 0, a 2<DD;
D;
[email protected] * pot@xD, funV@@1DD ^ 2, funV@@2DD ^ 2, funV@@3DD ^ 2<, 8x, -a 2, a 2<,
Box1D_Variational_Pot_NO_Symmetric.nb 3
For funV@1D: Ρ between -a2 and 0 = 0.265678 and Ρ between 0 and a2 = 0.734322
-0.4 -0.2 0.0 0.2 0.4
H* Verify the orthonormality of variational functions *L

overlap = Table@0, 8i, nf<, 8j, nf<D;
For@i = 1, i £ nf, i ++,
For@j = i, j £ nf, j ++,
overlap@@i, jDD =
NIntegrate@funV@@iDD * funV@@jDD, 8x, -a 2, 0, a 2<, AccuracyGoal ® 8D Chop;
If@j ¹ i, overlap@@j, i DD = overlap@@i, jDDD;
D;
D;
Print@"Overlap Mat variational fun = ", MatrixForm@overlapD ChopD
1. 0. ´ 10-10 0. ´ 10-10 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9

0. ´ 10-10 1. 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9
-10 -9 -9 -9 -9
0. ´ 10 0. ´ 10 1. 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10-9
0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 1. 0. ´ 10-9 0. ´ 10-9 0. ´ 10-10
-9 -9 -9 -9 -10
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 1. 0. ´ 10 0. ´ 10-9
0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-10 1. 0. ´ 10-9
Overlap Mat variational fun = -9 -9 -9 -10 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 1.
-9 -9 -10 -9 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10-9
0. ´ 10-9 0. ´ 10-10 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9
-10 -9 -9 -9 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10-9
0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9
-9 -9 -9 -9 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10-9
H* 3. Nondegenerate Perturbation Theory Time-
Independent for a Symmetric Potential applied in a One-dimensional Box *L
H* The length of the box *L

a = 1.0;
H* ne is nth-state perturbed and lon is the number

of states used to calculate the perturbation of each state *L
ne = 5;
lon = 20;
H* Vmin is the minimum value V0 so R will be greater than a2 *L

V0 = Input@"Introduce un valor de V0 menor que a2"D;
H* For a symmetric pontential regarding the centre of the box *L

R = HV0 ^ 2 + a ^ 2 4L H2 * V0L;
pot@x_D := R - Sqrt@R ^ 2 - x ^ 2D;
H* Introducing the general equations of the system *L

fx@nx_D :=
ham@fi_D := -H1 2.0L * D@fi, 8x, 2<D;
E0@ii_D := ham@fx@iiDD fx@iiD Chop;
E1@ii_D := NIntegrate@fx@iiD * pot@xD * fx@iiD, 8x, -a 2, a 2<D Chop;
H* The first and second correction energies *L

For@i = 1, i £ ne, i ++,
E2@iD = 0;
For@j = 1, j £ lon, j ++,
If@E0@jD ¹ E0@iD,
as = NIntegrate@fx@jD * pot@xD * fx@iD, 8x, -a 2, a 2<D Chop;
as1 = E0@iD - E0@jD;
E2@iD = E2@iD + as ^ 2 as1D;
D;
Print@"nx=", i, " E0@", i, "D=", E0@iD, " E1@", i, "D = ",
E1@iD, " E2@", i, "D=", E2@iD, " E@", i, "D=", E1@iD + E2@iD + E0@iDD
D;
nx=1 E0@1D=4.9348 E1@1D = 0.0361471 E2@1D=-0.0000517133 E@1D=4.9709
nx=2 E0@2D=19.7392 E1@2D = 0.0807531 E2@2D=-0.0000558346 E@2D=19.8199
nx=3 E0@3D=44.4132 E1@3D = 0.0925738 E2@3D=2.31083 ´ 10-7 E@3D=44.5058

-6
nx=4 E0@4D=78.9568 E1@4D = 0.0976427 E2@4D=9.74261 ´ 10 E@4D=79.0545
nx=5 E0@5D=123.37 E1@5D = 0.10035 E2@5D=0.0000103024 E@5D=123.47
2 Box1D_Perturb_Pot_Symmetric.nb
H* Obtaining the First-Order Wave-Functions Corrections *L

hij@i_, j_D := NIntegrate@fx@iD * pot@xD * fx@jD, 8x, -a 2, a 2<D Chop;
c@kk_, ii_D := hij@kk, iiD HE0@kkD - E0@iiDL;
For@k = 1, k £ ne, k ++,
li = k - 1; ls = k + 1;
fk = fx@kD + Sum@c@k, iD * fx@iD, 8i, 1, li<D + Sum@c@k, iD * fx@iD, 8i, ls, lon<D;
cte = 1 NIntegrate@fk ^ 2, 8x, -a 2, 0, a 2<D;
fun@kD = Sqrt@cteD * fk Expand Chop;
D;
H* Verifying non orthogonality of the perturbed functions *L

overlap = Table@0, 8i, ne<, 8j, ne<D;
For@i = 1, i £ ne, i ++,
For@j = i, j £ ne, j ++,
overlap@@i, jDD =
NIntegrate@fun@iD * fun@jD, 8x, -a 2, 0, a 2<, AccuracyGoal ® 8D Chop;
If@j ¹ i, overlap@@j, iDD = overlap@@i, jDDD;
D;
D;
MatrixForm@overlapD
1. 0. ´ 10-9 -8.00765 ´ 10-8 0. ´ 10-10 -8.67477 ´ 10-7

-9 -10 -8
0. ´ 10 1. 0. ´ 10 -7.22136 ´ 10 0. ´ 10-9
-8.00765 ´ 10-8 0. ´ 10-10 1. 0. ´ 10-9 -1.70396 ´ 10-7
0. ´ 10-10 -7.22136 ´ 10-8 0. ´ 10-9 1. 0. ´ 10-9
-7 -9 -7 -9
-8.67477 ´ 10 0. ´ 10 -1.70396 ´ 10 0. ´ 10 1.
H* The shape of the probabilities of the perturbed

functions and the symmetric distribution of charge density *L
For@i = 1, i £ ne, i ++,
Print@"For fun@", i, "D: Ρ between -a2 and 0 = ", NIntegrate@fun@iD ^ 2, 8x, -a 2, 0<D,
" and Ρ between 0 and a2 = ", NIntegrate@fun@iD ^ 2, 8x, 0, a 2<DD;
D;
Plot@8pot@xD, fun@1D ^ 2, fun@2D ^ 2, fun@3D ^ 2<, 8x, -a 2, a 2<,
Box1D_Perturb_Pot_Symmetric.nb 3
-0.4 -0.2 0.0 0.2 0.4
H* The shape of the perturbed functions with a symmetric potential applied *L
Plot@8pot@xD, fun@1D, fun@2D, fun@3D<, 8x, -a 2, a 2<,

-0.4 -0.2 0.0 0.2 0.4

H* 4. Linear Variation Method for
a Symmetric Potential applied in a One-dimensional Box *L
H* Introducing dates and wavefunction equation *L

nf = 12;
a = 1.0;
fi@nx_D :=
H* Vmin is the minimum value of V0 so R will be greater than a2 *L

V0 = Input@"Introduce un valor de V0 menor que a2"D;
H* For a symmetric potential regarding to the centre of the box *L

R = HV0 ^ 2 + a ^ 2 4L H2 * V0L;
pot@x_D := R - Sqrt@R ^ 2 - x ^ 2D;
H* Defining the hamiltonian operator *L

ham@fi_D := H-1 2.0L * D@fi, 8x, 2<D + pot@xD * fi;
H* Building the matrix *L

mat = Table@0, 8i, nf<, 8j, nf<D;
For@i = 1, i £ nf, i ++,
For@j = i, j £ nf, j ++,
mat@@i, jDD = NIntegrate@fi@iD * ham@fi@jDD, 8x, -a 2, 0, a 2<, AccuracyGoal ® 10D;
If@j ¹ i, mat@@j, iDD = mat@@i, jDDD;
D;
D;
H* Matrix diagonalization *L
ene = Eigenvalues@matD Chop;
vec = Eigenvectors@matD Chop;
H* Ordering of energies an vectors from lowest to highest *L

For@i = 1, i £ nf - 1, i ++,
For@j = i + 1, j £ nf, j ++,
ei = ene@@iDD; ej = ene@@jDD;
If@ej < ei, ene@@iDD = ej; ene@@jDD = ei; vec@@iDD = vecj; vec@@jDD = veciD;
D;
D;
H* The graphic plot of the symmetric potential applied *L

Plot@pot@xD, 8x, -a 2, a 2<, PlotRange ® All,
PlotStyle ® [email protected], Axes ® 8True, False<,
ene
2 Box1D_Variational_Pot_Symmetric.nb
-0.4 -0.2 0.0 0.2 0.4
84.9709, 19.8199, 44.5058, 79.0545, 123.47,

177.755, 241.908, 315.931, 399.823, 493.585, 597.216, 710.717<
H* Building a column vector with basis functions *L

fbasis = Table@0, 8i, nf<D;
For@i = 1, i £ nf, i ++,
fbasis@@iDD = fi@iD;
D;
H* Obtaining the variational functions *L funV = vec.fbasis;
Plot@8funV@@1DD, funV@@2DD, funV@@3DD, pot@xD<, 8x, -a 2, a 2<,

-0.4 -0.2 0.0 0.2 0.4
H* Verify the symmetric distribution of charge density of the

variational functions as consequence symmetric potential applied *L
For@i = 1, i £ 6, i ++,
Print@"For funV@", i,
"D: Ρ between -a2 and 0 = ", NIntegrate@funV@@iDD ^ 2, 8x, -a 2, 0<D,
" and Ρ between 0 and a2 = ", NIntegrate@funV@@iDD ^ 2, 8x, 0, a 2<DD;
D;
Plot@8pot@xD, funV@@1DD ^ 2, funV@@2DD ^ 2, funV@@3DD ^ 2<, 8x, -a 2, a 2<,
Box1D_Variational_Pot_Symmetric.nb 3
-0.4 -0.2 0.0 0.2 0.4
H* Verify the orthonormality of variational functions *L

overlap = Table@0, 8i, nf<, 8j, nf<D;
For@i = 1, i £ nf, i ++,
For@j = i, j £ nf, j ++,
overlap@@i, jDD =
NIntegrate@funV@@iDD * funV@@jDD, 8x, -a 2, 0, a 2<, AccuracyGoal ® 8D Chop;
If@j ¹ i, overlap@@j, i DD = overlap@@i, jDDD;
D;
D;
Print@"Overlap Mat variational fun = ", MatrixForm@overlapDD
1. 0. ´ 10-9 0. ´ 10-9 0. ´ 10-10 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9

0. ´ 10-9 1. 0. ´ 10-10 0. ´ 10-9 0. ´ 10-9 0. ´ 10-10 0. ´ 10-9
-9 -10 -9 -10
0. ´ 10 0. ´ 10 1. 0. ´ 10 0. ´ 10 0. ´ 10-9 0. ´ 10-10
0. ´ 10-10 0. ´ 10-9 0. ´ 10-9 1. 0. ´ 10-9 0. ´ 10-10 0. ´ 10-10
-9 -9 -10 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 1. 0. ´ 10-10 0. ´ 10-9
0. ´ 10-9 0. ´ 10-10 0. ´ 10-9 0. ´ 10-10 0. ´ 10-10 1. 0. ´ 10-9
Overlap Mat variational fun = -9 -9 -10 -10 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 1.
-9 -10 -10 -9 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10-9
0. ´ 10-10 0. ´ 10-10 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0
-9 -9 -9 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0. ´ 10 0 0. ´ 10-9
0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0. ´ 10-9 0 0. ´ 10-9 0. ´ 10-9
-9 -9 -9 -9 -9
0. ´ 10 0. ´ 10 0. ´ 10 0 0. ´ 10 0. ´ 10 0. ´ 10-9
H* 5. Selection Rules of Transitions *L
H* To hartree from joules *L

a = 1;
fi@nx_D :=
n = 10;
ini = 1;
filas = Sum@n - i, 8i, 1, ini<D;
tabla = Table@0, 8i, filas<, 8j, 4<D;
m12 = H2 * Pi 3L * Integrate@fi@1D * x * fi@2D, 8x, -a 2, a 2<D N Chop;
contador = 1;
For@i = 1, i £ ini, i ++,
For@f = i + 1, f £ n, f += 1,
as1 = H2 * Pi 3L * Integrate@fi@iD * x * fi@fD, 8x, -a 2, a 2<D N Chop;
as2 = Has1 m12L ^ 2;
tabla@@contador, 1DD = i;
tabla@@contador, 2DD = f;
tabla@@contador, 3DD = Abs@as1D;
tabla@@contador, 4DD = as2;
contador = contador + 1;
D;
D;
H* Integral values of <fi@iD*x*fi@fD> *L

TableFormAtabla,
TableHeadings ® 9None, 9"Est i", "Est f", "ÈΜnm È", "Μnm 2 Μ1,2 2 "==, TableAlignments ® LeftE
Est i Est f ÈΜnm È Μnm 2 Μ1,2 2

1 2 0.377256 1.
1 3 0 0.
1 4 0.0301805 0.0064
1 5 0 0.
1 6 0.00831503 0.000485798
1 7 0 0.
1 8 0.00342182 0.0000822702
1 9 0 0.
1 10 0.00173212 0.0000210807
6. COMSOL images
H∗ 9. Nondegenerate Perturbation Theory Time−Independent applied
for an Asymmetric Potential applied in a Two−dimensional Box ∗L
ClearAll@"Global`∗"D;
H∗ Rectangular box a ≠ b, to avoid accidental degeneracies ∗L

a = 1.0;
b = 1.2;
nn = 3;
H∗ Creating a list of complete set of functions ∗L

lista = 8<;
funlis = 8<;
H∗ Introducing functions of the system ∗L

For@i = 1, i ≤ nn, i ++,
For@j = 1, j ≤ nn, j ++,
lista = AppendTo@lista, 8i, j<D;
D;
D;
lon = Length@listaD;
fx@nx_D :=
If@OddQ@nxD True, Sqrt@2 ê aD ∗ Cos@nx ∗ Pi ∗ x ê aD, Sqrt@2 ê aD ∗ Sin@nx ∗ Pi ∗ x ê aDD;
fy@ny_D := If@OddQ@nyD True, Sqrt@2 ê bD ∗ Cos@ny ∗ Pi ∗ y ê bD,
Sqrt@2 ê bD ∗ Sin@ny ∗ Pi ∗ y ê bDD;
fxy@nx_, ny_D := fx@nxD ∗ fy@nyD;
For@i = 1, i ≤ lon, i ++,
funlis = AppendTo@funlis, fxy@lista@@i, 1DD, lista@@i, 2DDDD;
D;
H∗ Introducing the big asymmetric potential ∗L

pot@x_, y_D := 4.15 ∗ Exp@− 2.5 ∗ HHx + 0.2L ^ 2 + yLD;
H∗ Introducing the small asymmetric potential ∗L
H∗ pot@x_,y_D:=0.15∗Exp@−2.5∗HHx+0.2L^2+yLD; ∗L
H∗ The first and second energies corrections ∗L

ham@fxy_D := − H1 ê 2.0L ∗ HD@fxy, 8x, 2<D + D@fxy, 8y, 2<DL;
E0@ii_D := ham@funlis@@iiDDD ê funlis@@iiDD êê FullSimplify êê Chop;
E1@ii_D := NIntegrate@Expand@funlis@@iiDD ∗ pot@x, yD ∗ funlis@@iiDDD,
8x, − a ê 2, 0, a ê 2<, 8y, − b ê 2, 0, b ê 2<, Method → "LocalAdaptive",
AccuracyGoal → 6, PrecisionGoal → 6D êê Chop;
tabla = Table@0, 8i, lon<, 8j, 6<D;
For@i = 1, i ≤ lon, i ++,
E2@iD = 0;
For@j = 1, j ≤ lon, j ++,
If@E0@jD ≠ E0@iD,
as =
NIntegrate@funlis@@jDD ∗ pot@x, yD ∗ funlis@@iDD, 8x, − a ê 2, 0, a ê 2<, 8y, − b ê 2, 0,
b ê 2<, Method → "LocalAdaptive", AccuracyGoal → 6, PrecisionGoal → 6D êê Chop;
as1 = E0@iD − E0@jD;
E2@iD = E2@iD + as ^ 2 ê as1D;
D;
Etot@iD = E1@iD + E2@iD + E0@iD;
2 Box_Rectang_Perturb_Pot_NO_Symmetric.nb
tabla@@iDD = 8lista@@i, 1DD, lista@@i, 2DD, E0@iD, E1@iD, E2@iD, Etot@iD<;

D;
H∗ Output with the first and second energy corrections

and the total energy values of the perturbed functions ∗L
TableFormAtabla, TableAlignments → Left,
TableHeadings → 9None, 9"nx", "ny", "EH0L ", "EH1L ", "EH2L ", "E"==E
nx ny EH0L EH1L EH2L E

1 1 8.36175 4.07721 − 0.494139 11.9448
1 2 18.6426 4.73674 0.0171189 23.3964
1 3 35.7773 4.88302 0.385524 41.0459
2 1 23.1662 3.78249 − 0.35849 26.5902
2 2 33.447 4.39435 0.0228341 37.8642
2 3 50.5817 4.53005 0.321246 55.433
3 1 47.8402 3.74184 − 0.360941 51.2211
3 2 58.121 4.34712 0.128402 62.5965
3 3 75.2557 4.48136 0.338445 80.0755
H∗ Graphic plot of the pontentual applied ∗L

Plot3D@pot@x, yD, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<,
PlotRange → All, PlotStyle → [email protected], Axes → 8False, False<,
AxesStyle → Directive@Black, [email protected], Filling −> Axis, AspectRatio → 0.5D
Box_Rectang_Perturb_Pot_NO_Symmetric.nb 3
H∗ Obtaining the First−Order Wave−

Functions Corrections to first perturbation order ∗L
nf = 5;
hij@i_, j_D := NIntegrate@funlis@@iDD ∗ pot@x, yD ∗ funlis@@jDD, 8x, − a ê 2, 0, a ê 2<,
8y, − b ê 2, 0, b ê 2<, AccuracyGoal → 4, PrecisionGoal → 6D êê Chop;
EE0@ii_D := ham@funlis@@iiDDD ê funlis@@iiDD êê FullSimplify êê Chop;
c@kk_, ii_D := hij@kk, iiD ê HEE0@kkD − EE0@iiDL;
For@k = 1, k ≤ nf, k ++,
li = k − 1; ls = k + 1;
fk = funlis@@kDD + Sum@c@k, iD ∗ funlis@@iDD, 8i, 1, li<D +
Sum@c@k, iD ∗ funlis@@iDD, 8i, ls, lon<D; cte =
1 ê NIntegrate@fk ^ 2, 8x, − a ê 2, − a ê 4, 0, a ê 4, a ê 2<, 8y, − b ê 2, − b ê 4, 0, b ê 4, b ê 2<,
Method → "LocalAdaptive", AccuracyGoal → 6, PrecisionGoal → 6D;
fun@kD = Sqrt@cteD ∗ fk êê Expand êê Chop;
D;
H∗ Verifying non orthogonality of the perturbed functions ∗L

solap = Table@0, 8i, nf<, 8j, nf<D;
For@i = 1, i ≤ nf, i ++,
For@j = i, j ≤ nf, j ++,
solap@@i, jDD = NIntegrate@fun@iD ∗ fun@jD,
8x, − a ê 2, − a ê 4, 0, a ê 4, a ê 2<, 8y, − b ê 2, − b ê 4, 0, b ê 4, b ê 2<,
Method → "LocalAdaptive", AccuracyGoal → 6, PrecisionGoal → 5D êê Chop;
If@j ≠ i, solap@@j, iDD = solap@@i, jDDD;
D;
D;
MatrixForm@solapD
1. − 0.00722722 0.0305527 0.0125515 − 0.0142267
− 0.00722722 1. − 0.00348536 0.0193342 − 0.0126473
0.0305527 − 0.00348536 1. − 0.0187825 − 0.014968
0.0125515 0.0193342 − 0.0187825 1. − 0.00926794
− 0.0142267 − 0.0126473 − 0.014968 − 0.00926794 1.
For@i = 1, i ≤ lon − 1, i ++,
For@j = i + 1, j ≤ lon, j ++,
eni = Etot@iD; enj = Etot@jD; funi = fun@iD;
funj = fun@jD; lisi = lista@@iDD; lisj = lista@@jDD;
If@enj < eni, Etot@iD = enj; Etot@jD = eni; fun@iD = funj;
fun@jD = funi; lista@@iDD = lisj; lista@@jDD = lisiD;
D;
D;
For@i = 1, i ≤ nf, i ++,
Print@"nx=", lista@@i, 1DD, " ny=", lista@@i, 2DD,
" E@", lista@@i, 1DD, ",", lista@@i, 2DD, "D=", Etot@iDD;
D;
nx=1 ny=1 E@1,1D=11.9448
nx=1 ny=2 E@1,2D=23.3964
nx=2 ny=1 E@2,1D=26.5902
nx=2 ny=2 E@2,2D=37.8642
nx=1 ny=3 E@1,3D=41.0459

4 Box_Rectang_Perturb_Pot_NO_Symmetric.nb
H∗ Veryfying the asymmetric distributions

of charge density in the perturbed functions ∗L
For@i = 1, i ≤ nf, i ++,
Print@"Para fun ", lista@@iDD, ": ρ entre −aê2 y 0 = ",
NIntegrate@fun@iD ^ 2, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, 0<D, " y ρ entre 0 y aê2 = ",
NIntegrate@fun@iD ^ 2, 8x, − a ê 2, a ê 2<, 8y, 0, b ê 2<DD;
D;
Para fun 81, 1<: ρ entre −aê2 y 0 = 0.334844 y ρ entre 0 y aê2 = 0.665156
H∗ Shape of the probabilities ∗L

[email protected] ∗ pot@x, yD, Etot@1D + fun@1D,
Etot@2D + fun@2D, Etot@3D + fun@3D, Etot@4D + fun@4D<, 8x, − a ê 2, a ê 2<,
8y, − b ê 2, b ê 2<, PlotRange → All, BoxRatios → 81, 1, 4<, Axes → FalseD
H∗ Other shapes of perturbed functions ∗L

For@i = 1, i ≤ nf, i ++,
Print@"Energia estado ", i, " = ", Etot@iDD Print@ContourPlot@fun@iD, 8x, − a ê 2, a ê 2<,
8y, − b ê 2, b ê 2<, AspectRatio → b ê a, BoundaryStyle → Directive@Red, ThickDDD
D;
Box_Rectang_Perturb_Pot_NO_Symmetric.nb 5
Energia estado 1 = 11.9448

H∗ 11. Linear Variation Method for
an Asymmetric Potential applied in a Two−dimensional Box ∗L
H∗ Dimensions of rectangular box and number of functions ∗L

a = 1.0;
b = 1.2;
nn = 3;

lisfun = 8<;
H∗ Introducing the big asymmetric potential and

the corresponding wave functions for a two−dimensional box ∗L
pot@x_, y_D := 4.15 ∗ Exp@− 2.5 ∗ HHx + 0.2L ^ 2 + yLD;
H∗ Introducing the small asymmetric potential and
the corresponding wave functions for a two−dimensional box ∗L
H∗ pot@x_,y_D:=0.15∗Exp@−2.5∗HHx+0.2L^2+yLD; ∗L
fx@nx_D :=
ham@fun_D := − H1 ê 2.0L ∗ HD@fun, 8x, 2<D + D@fun, 8y, 2<DL + pot@x, yD ∗ fun;
For@i = 1, i ≤ nn, i ++,
For@j = 1, j ≤ nn, j ++,
lisfun = AppendTo@lisfun, fxy@i, jDD;
D;
D;
H∗ Hamiltonian matrix ∗L
lon = Length@lisfunD;
mat = Table@0, 8i, lon<, 8j, lon<D;
For@i = 1, i ≤ lon, i ++,
For@j = i, j ≤ lon, j ++,
mat@@i, jDD = Integrate@
lisfun@@iDD ∗ ham@lisfun@@jDDD, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<D êê Chop;
mat@@j, iDD = mat@@i, jDD;
D;
D;
H∗ Matrix diagonalization ∗L
ene = Eigenvalues@matD;
vec = Eigenvectors@matD;
For@i = 1, i ≤ lon − 1, i ++,
For@j = i + 1, j ≤ lon, j ++,
enei = ene@@iDD; enej = ene@@jDD;
If@enej < enei,
ene@@iDD = enej; ene@@jDD = enei;
vec@@iDD = vecj; vec@@jDD = veci;
D;
D;
D
2 Box_Rectang_Variational_Pot_NO_Symmetric.nb
D;
Print@" "D;
Print@"Potencial fondo caja"D;
H∗ Graphic plot of big asymmetric potential applied ∗L

Plot3D@pot@x, yD, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<,
PlotRange → All, PlotStyle → [email protected], Axes → 8True, False<,
AxesStyle → Directive@Black, [email protected], Filling −> Axis, AspectRatio → 0.5D
Print@" "D;
fun = vec.lisfun;
For@i = 1, i ≤ lon, i ++,
Print@"Energia estado ", i, " = ", ene@@iDDD
H∗Print@Plot3D@fun@@iDD,8x,−aê2,aê2<,8y,−bê2,bê2<DD;Print@ContourPlot@
fun@@iDD,8x,−aê2,aê2<,8y,−bê2,bê2<,BoundaryStyle→Directive@Red,ThickDDD;
Print@" "D;∗L
D;
Potencial fondo caja

Box_Rectang_Variational_Pot_NO_Symmetric.nb 3
H∗ Verify the orthogonality of the first nf functions ∗L

nf = 5;
For@i = 1, i ≤ nf, i ++,
For@j = i, j ≤ nf, j ++,
solap@@i, jDD = NIntegrate@fun@@iDD ∗ fun@@jDD,
D;
D;
MatrixForm@solapD
1. 0 0 0 0
0 1. 0 0 0
0 0 1. 0 0
0 0 0 1. 0
0 0 0 0 1.
H∗ Verify the big asymmetric distribution of charge density of the

variational functions as consequence big asymmetric potential applied ∗L
For@i = 1, i ≤ nf, i ++,
Print@"Para funcion ", i, ": ρ entre −aê2 y 0 = ",
NIntegrate@fun@@iDD ^ 2, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, 0<D, " y ρ entre 0 y aê2 = ",
NIntegrate@fun@@iDD ^ 2, 8x, − a ê 2, a ê 2<, 8y, 0, b ê 2<DD;
D;
Para funcion 1: ρ entre −aê2 y 0 = 0.349907 y ρ entre 0 y aê2 = 0.650093

4 Box_Rectang_Variational_Pot_NO_Symmetric.nb
H∗ Graphic plots of the variational functions ∗L

Plot3D@8ene@@1DD + fun@@1DD, ene@@2DD + fun@@2DD,
ene@@3DD + fun@@3DD, ene@@4DD + fun@@4DD<, 8x, − a ê 2, a ê 2<,
8y, − b ê 2, b ê 2<, PlotRange → All, BoxRatios → 82, 2, 4<, Axes → FalseD
H∗ Graphic plots of the distorted variational functions

with the corresponding energy values of the states ∗L
For@i = 1, i ≤ nf, i ++,
Print@"Energia estado ", i, " = ", ene@@iDDD Print@ContourPlot@fun@@iDD,
8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<, BoundaryStyle → Directive@Red, ThickDDD
D;
Box_Rectang_Variational_Pot_NO_Symmetric.nb 5

In[1]:=
H∗ 13. Nondegenerate Perturbation Theory Time

−Independent applied for a Symmetric Potential applied in a Two−dimensional Box ∗L
H∗ Rectangular box a ≠ b, to avoid accidental degeneracies ∗L

a = 1.0;
b = 1.2;
nn = 3;

lista = 8<;
funlis = 8<;
H∗ Introducing functions of the system ∗L

For@i = 1, i ≤ nn, i ++,
For@j = 1, j ≤ nn, j ++,
lista = AppendTo@lista, 8i, j<D;
D;
D;
lon = Length@listaD;
fx@nx_D :=
For@i = 1, i ≤ lon, i ++,
funlis = AppendTo@funlis, fxy@lista@@i, 1DD, lista@@i, 2DDDD;
D;
H∗ Vmin is the minimum value V0 so R will be greater than aê2 ∗L

V0 = Input@"Introduce un valor de V0 menor que aê2"D;
H∗ For a symmetric pontential regarding the centre of the box ∗L

R = HV0 ^ 2 + a ^ 2 ê 4L ê H2 ∗ V0L;
pot@x_, y_D := R − Sqrt@R ^ 2 − x ^ 2D;
H∗ Introducing the general equations of the system ∗L

ham@fxy_D := − H1 ê 2.0L ∗ HD@fxy, 8x, 2<D + D@fxy, 8y, 2<DL;
E0@ii_D := ham@funlis@@iiDDD ê funlis@@iiDD êê FullSimplify êê Chop;
E1@ii_D := NIntegrate@Expand@funlis@@iiDD ∗ pot@x, yD ∗ funlis@@iiDDD,
8x, − a ê 2, 0, a ê 2<, 8y, − b ê 2, 0, b ê 2<, Method → "LocalAdaptive",
AccuracyGoal → 6, PrecisionGoal → 6D êê Chop;
tabla = Table@0, 8i, lon<, 8j, 6<D;
H∗ The first and second correction energies ∗L

For@i = 1, i ≤ lon, i ++,
E2@iD = 0;
For@j = 1, j ≤ lon, j ++,
If@E0@jD ≠ E0@iD,
as =
NIntegrate@funlis@@jDD ∗ pot@x, yD ∗ funlis@@iDD, 8x, − a ê 2, 0, a ê 2<, 8y, − b ê 2, 0,
as1 = E0@iD − E0@jD;
E2@iD = E2@iD + as ^ 2 ê as1D;
D
2 Box_Rectang_Perturb_Pot_Symmetric.nb
D;
Etot@iD = E1@iD + E2@iD + E0@iD;
tabla@@iDD = 8lista@@i, 1DD, lista@@i, 2DD, E0@iD, E1@iD, Chop@E2@iDD, Etot@iD<;
D;
TableFormAtabla, TableAlignments → Left,
TableHeadings → 9None, 9"nx", "ny", "EH0L ", "EH1L ", "EH2L ", "E"==E
Out[21]//TableForm=
nx ny EH0L EH1L EH2L E
1 1 8.36175 0.0361471 − 0.0000503998 8.39784
1 2 18.6426 0.0361471 − 0.0000503999 18.6787
1 3 35.7773 0.0361471 − 0.0000503998 35.8134
2 1 23.1662 0.0807532 0 23.2469
2 2 33.447 0.0807533 0 33.5277
2 3 50.5817 0.0807532 0 50.6625
3 1 47.8402 0.092574 0.0000503998 47.9328
3 2 58.121 0.0925738 0.0000503999 58.2136
3 3 75.2557 0.0925738 0.0000503998 75.3484
In[22]:= Print@" "D;
Print@"Perturbación = ", pot@x, yDD;
H∗ Shape of the symmetric potential ∗L

Plot3D@pot@x, yD, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<, PlotRange → AllD
Perturbación = 0.5 − 0.25 − x2
Out[24]=
Box_Rectang_Perturb_Pot_Symmetric.nb 3
In[25]:= H∗ Obtaining the First−Order Wave−

Functions Corrections to first perturbation order ∗L
nf = lon;
hij@i_, j_D := NIntegrate@funlis@@iDD ∗ pot@x, yD ∗ funlis@@jDD, 8x, − a ê 2, 0, a ê 2<,
8y, − b ê 2, 0, b ê 2<, AccuracyGoal → 4, PrecisionGoal → 6D êê Chop;
EE0@ii_D := ham@funlis@@iiDDD ê funlis@@iiDD êê FullSimplify êê Chop;
c@kk_, ii_D := hij@kk, iiD ê HEE0@kkD − EE0@iiDL;
For@k = 1, k ≤ nf, k ++,
li = k − 1; ls = k + 1;
fk = funlis@@kDD + Sum@c@k, iD ∗ funlis@@iDD, 8i, 1, li<D +
Sum@c@k, iD ∗ funlis@@iDD, 8i, ls, lon<D; cte =
1 ê NIntegrate@fk ^ 2, 8x, − a ê 2, − a ê 4, 0, a ê 4, a ê 2<, 8y, − b ê 2, − b ê 4, 0, b ê 4, b ê 2<,
Method → "LocalAdaptive", AccuracyGoal → 6, PrecisionGoal → 6D;
fun@kD = Sqrt@cteD ∗ fk êê Expand êê Chop;
D;
H∗ Verifying orthogonality of the perturbed functions ∗L

solap = Table@0, 8i, lon<, 8j, lon<D;
For@i = 1, i ≤ nf, i ++,
For@j = i, j ≤ nf, j ++,
solap@@i, jDD = NIntegrate@fun@iD ∗ fun@jD,
D;
D;
MatrixForm@solapD
Out[32]//MatrixForm=
1. 0 0 0 0 0 0 0 0
0 1. 0 0 0 0 0 0 0
0 0 1. 0 0 0 0 0 0
0 0 0 1. 0 0 0 0 0
0 0 0 0 1. 0 0 0 0
0 0 0 0 0 1. 0 0 0
0 0 0 0 0 0 1. 0 0
0 0 0 0 0 0 0 1. 0
0 0 0 0 0 0 0 0 1.
In[33]:= For@i = 1, i ≤ lon − 1, i ++,
For@j = i + 1, j ≤ lon, j ++,
eni = Etot@iD; enj = Etot@jD; funi = fun@iD;
funj = fun@jD; lisi = lista@@iDD; lisj = lista@@jDD;
If@enj < eni, Etot@iD = enj; Etot@jD = eni; fun@iD = funj;
fun@jD = funi; lista@@iDD = lisj; lista@@jDD = lisiD;
D;
D;
For@i = 1, i ≤ nf, i ++,
Print@"nx=", lista@@i, 1DD, " ny=", lista@@i, 2DD,
" E@", lista@@i, 1DD, ",", lista@@i, 2DD, "D=", Etot@iDD;
D;
nx=1 ny=1 E@1,1D=8.39784
nx=1 ny=2 E@1,2D=18.6787
nx=2 ny=1 E@2,1D=23.2469
nx=2 ny=2 E@2,2D=33.5277
nx=1 ny=3 E@1,3D=35.8134
nx=3 ny=1 E@3,1D=47.9328
nx=2 ny=3 E@2,3D=50.6625
nx=3 ny=2 E@3,2D=58.2136
nx=3 ny=3 E@3,3D=75.3484
In[35]:=
H∗ The shape of the probabilities of the perturbed

functions and the symmetric distribution of charge density ∗L
For@i = 1, i ≤ nf, i ++,
Print@"Para fun ", lista@@iDD, ": ρ entre −aê2 y 0 = ",
NIntegrate@fun@iD ^ 2, 8x, − a ê 2, 0<, 8y, − b ê 2, b ê 2<D, " y ρ entre 0 y aê2 = ",
NIntegrate@fun@iD ^ 2, 8x, 0, a ê 2<, 8y, − b ê 2, b ê 2<DD;
D;
Box_Rectang_Perturb_Pot_Symmetric.nb 5
In[36]:= Plot3D@83 ∗ fun@1D, Etot@2D + fun@2D, Etot@3D + fun@3D, Etot@4D + fun@4D<,

8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<, BoxRatios → 82, 2, 5<, Axes → FalseD
Out[36]=
In[37]:= H∗ Other shapes of perturbed functions ∗L

For@i = 1, i ≤ nf, i ++,
Print@"Energia estado ", i, " = ", Etot@iDD
Print@ContourPlot@fun@iD, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<,
AspectRatio → b ê a, BoundaryStyle → Directive@Red, ThickDDD
D;

H∗ 14. Linear Variation Method for
a Symmetric Potential applied in a Two−dimensional Box ∗L
H∗ Dimensions of rectangular box and number of functions ∗L

a = 1.0;
b = 1.2;
nn = 3;

lisfun = 8<;
H∗ Vmin is the minimum value of V0 so R will be greater than aê2 ∗L

V0 = Input@"Introduce un valor de V0 menor que aê2"D;
H∗ For a symmetric potential regarding to the centre of the box ∗L

R = HV0 ^ 2 + a ^ 2 ê 4L ê H2 ∗ V0L;
pot@x_, y_D := R − Sqrt@R ^ 2 − x ^ 2D;
H∗ Introducing the corresponding wave functions for a two

−dimensional box and the hamiltonian operator ∗L
fx@nx_D := If@OddQ@nxD True, Sqrt@2 ê aD ∗ Cos@nx ∗ Pi ∗ x ê aD,
Sqrt@2 ê aD ∗ Sin@nx ∗ Pi ∗ x ê aDD;
ham@fun_D := − H1 ê 2.0L ∗ HD@fun, 8x, 2<D + D@fun, 8y, 2<DL + pot@x, yD ∗ fun;
For@i = 1, i ≤ nn, i ++,
For@j = 1, j ≤ nn, j ++,
lisfun = AppendTo@lisfun, fxy@i, jDD;
D;
D;
H∗ Hamiltonian matrix ∗L
lon = Length@lisfunD;
mat = Table@0, 8i, lon<, 8j, lon<D;
For@i = 1, i ≤ lon, i ++,
For@j = i, j ≤ lon, j ++,
mat@@i, jDD = NIntegrate@lisfun@@iDD ∗ ham@lisfun@@jDDD, 8x, − a ê 2, a ê 2<, 8y, − b ê 2,
mat@@j, iDD = mat@@i, jDD;
D;
D;
H∗ Matrix diagonalization ∗L
ene = Eigenvalues@matD;
vec = Eigenvectors@matD;
For@i = 1, i ≤ lon − 1, i ++,
For@j = i + 1, j ≤ lon, j ++,
2 Box_Rectang_Variational_Pot_Symmetric.nb
enei = ene@@iDD; enej = ene@@jDD;

If@enej < enei,
ene@@iDD = enej; ene@@jDD = enei;
vec@@iDD = vecj; vec@@jDD = veci;
D;
D;
D;
Print@" "D;
Print@"Potencial fondo caja"D;
H∗ Graphic plot of symmetric potential applied ∗L

Plot3D@pot@x, yD, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<, PlotRange → AllD
Print@" "D;
fun = vec.lisfun;
For@i = 1, i ≤ lon, i ++,
Print@"Energia estado ", i, " = ", ene@@iDDD
D;
Potencial fondo caja

Box_Rectang_Variational_Pot_Symmetric.nb 3
H∗ Verify the orthogonality of the first nf functions ∗L

nf = 5;
For@i = 1, i ≤ nf, i ++,
For@j = i, j ≤ nf, j ++,
solap@@i, jDD = NIntegrate@fun@@iDD ∗ fun@@jDD,
D;
D;
MatrixForm@solapD
1. 0 0 0 0
0 1. 0 0 0
0 0 1. 0 0
0 0 0 1. 0
0 0 0 0 1.
H∗ Verify the symmetric distribution of charge density of the

variational functions as consequence symmetric potential applied ∗L
For@i = 1, i ≤ nf, i ++,
Print@"Para funcion ", i, ": ρ entre −aê2 y 0 = ",
NIntegrate@fun@@iDD ^ 2, 8x, − a ê 2, a ê 2<, 8y, − b ê 2, 0<D, " y ρ entre 0 y aê2 = ",
NIntegrate@fun@@iDD ^ 2, 8x, − a ê 2, a ê 2<, 8y, 0, b ê 2<DD;
D;

4 Box_Rectang_Variational_Pot_Symmetric.nb
H∗ Graphic plots of the variational functions without any distorsion ∗L

Plot3D@8ene@@1DD + fun@@1DD, ene@@2DD + fun@@2DD, ene@@3DD + fun@@3DD, ene@@4DD + fun@@4DD<,
8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<, PlotRange → All, BoxRatios → 82, 2, 4<, Axes → FalseD
H∗ Graphic plots of the variational functions

with the corresponding energy values of the states ∗L
For@i = 1, i ≤ nf, i ++,
Print@"Energia estado ", i, " = ", ene@@iDDD Print@ContourPlot@fun@@iDD,
8x, − a ê 2, a ê 2<, 8y, − b ê 2, b ê 2<, BoundaryStyle → Directive@Red, ThickDDD
D;
Box_Rectang_Variational_Pot_Symmetric.nb 5

Physical Chemistry
6. References
[1] Levine, I. N., Quantum Chemistry, Prentice Hall: New York, 2000.
[2] El Issa, B.D., The Particle in a Box Revisited, J. Chem. Educ., 83, 781, 1998.
[3] Hollingsworth, C.A., Accidental Degeneracies of the Particle in a Box, J. Chem. Educ., 67, 999, 1990.
[4] Ying Q.Liang, Momentum Distributions for a Particle in a Box, J. Chem. Educ., 72, 148, 1995.
[5] R. Chang, Basic Principles of Spectroscopy, McGraw Hill, New York, 1971.
[6] Planelles, J., Spectroscopy, Jaume I University, Castellón de la Plana, 2002.
77

Particle in A Box Revisited-TFG Borja Rodrigo

Uploaded by

Copyright:

Available Formats

Particle in A Box Revisited-TFG Borja Rodrigo

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Particle in A Box Revisited-TFG Borja Rodrigo

Uploaded by

Copyright:

Available Formats

Jaume I University

Higher School of Technology and Experimental Science

Particle in a Box Revisited

2.1 Particle in a Box without Potential

2.1.1 Particle in a One-Dimensional Box

𝑥 = −𝑎/2 𝑥=0 𝑥 = 𝑎/2

being the Schrödinger equation for the system

1.41421cos 3.14159𝑥 1.41421sin 6.28319𝑥 1.41421cos 9.42478𝑥

The Figure 3 shows the shapes of the orthogonality basis functions

Figure 3. The shape of the functions 𝜳𝒊 𝜳𝒋 .

2.1.2 Particle in a Two-Dimensional Box

Figure 4. Particle in a two-dimensional box −𝒂/𝟐 ≤ 𝒙 ≤ 𝒂/𝟐 and −𝒃/𝟐 ≤ 𝒚 ≤ 𝒃/𝟐.

Based on the Eq. (8) can be considered 𝐻 ̂𝑥 + 𝐻

So, a complete set of functions used will be

𝛹𝑛𝑥 𝑛𝑦 𝑥, 𝑦 = 𝛹𝑛𝑥 𝑥 𝛹𝑛𝑦 𝑦 11

and the energy

The values of the exact energy, in a 2D box, are given by

𝛹11 𝛹12 𝛹22

1.82574cos 2.61799𝑦 sin 6.28319𝑥

𝐸12 = 24,674 𝐸21 = 24,674

2.2 Particle in a Box with Potential

2.2.1 Linear Variations Method

𝜙 = 𝑐1 𝛹1° + 𝑐2 𝛹2° + ⋯ + 𝑐𝑛 𝛹𝑛° = ∑ 𝑐𝑖 𝛹𝑖° 15

Then, through a little bit of algebra, we will get

where ℍ is the matrix

𝕊 is the overlap matrix

𝑆𝑖𝑗 = < 𝛹𝑖° |𝛹𝑗° > = 𝑆𝑗𝑖 19

2.2.2 Nondegenerate Perturbation Theory

̂ ° 𝛹𝑖° = 𝐸𝑖° 𝛹𝑖°

The Hamiltonian of perturbed system is represented by

It is important that 𝛹𝑖 satisfy

< 𝛹𝑖° |𝛹𝑖 >= 1 26

By a little bit of algebra, we will get the general term for 𝜆𝑛

The First-Order Energy Correction

multiplying by (𝛹𝑖° )* and integrating all space we have

1 ̂ ° − 𝐸𝑖° |𝛹𝑖 1 ̂ ′ |𝛹𝑖° >

1 ̂ ′ |𝛹𝑖° >= ∫ 𝛹𝑖°∗ 𝐻

The First-Order Wave-Function Correction

The Second-Order Energy Correction

2.3 Radiation/matter interaction

where 𝜇𝑛𝑚 , the transition dipole moment, is given by

𝜇𝑛𝑚 = ∫ 𝛹𝑛∗ 𝑥 𝜇𝛹𝑚 𝑥 𝑑𝑥 43

Asymmetric potential Symmetric potential

Table 1. Types of potential applied where 𝑹 = 𝑽𝟎 ^𝟐 + 𝒂^𝟐⁄𝟒 ⁄ 𝟐 ∗ 𝑽𝟎 .

The shape of the asymmetric potentials is:

Figure 8. The shape of the asymmetric potential 𝑽 𝒙 = 𝟒. 𝟓𝓮−𝟓.𝟓𝒙 in a one-dimensional box.

The shape of the symmetric potentials is:

3.1 Approximation by Linear Variation Method

3.1.1 Particle in a 1D System with 𝑽 ≠ 𝟎 inside the Box

𝒔.𝒂𝒔𝒚𝒎. 𝒃.𝒂𝒔𝒚𝒎. 𝒔𝒚𝒎.

𝒔.𝒂𝒔𝒚𝒎. 𝒃.𝒂𝒔𝒚𝒎. 𝒔𝒚𝒎.

3.1.2 Particle in a 2D System with 𝑽 ≠ 𝟎 inside the Box

Applying the symmetric potential, the shape of functions obtained were:

𝒔.𝒂𝒔𝒚𝒎. 𝒃.𝒂𝒔𝒚𝒎. 𝒔𝒚𝒎.

And the values of charge density

𝒔.𝒂𝒔𝒚𝒎. 𝒃.𝒂𝒔𝒚𝒎. 𝒔𝒚𝒎.

3.2 Approximation by Perturbation Theory Time-Independent

3.2.1 Particle in a 1D System with Perturbation inside the Box

̂ ′ the energies and

Plot@8pot@xD * 0.05, fun@1D, fun@2D, fun@3D<, 8x, -a 2, a 2<,

Plot@8funV@@1DD, funV@@2DD, funV@@3DD, pot@xD * 0.05<, 8x, -a 2, a 2<,

H* Vmin is the minimum value V0 so R will be greater than a2 *L

Plot@8pot@xD, fun@1D, fun@2D, fun@3D<, 8x, -a 2, a 2<,

H* Vmin is the minimum value of V0 so R will be greater than a2 *L