S. Keith Dunn
Department of Chemistry
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This exercise provides undergraduate physical chemistry students with an understandable introduction to the
Variational Method. Students use linear combinations of basis functions for finding approximate solutions to the
Schr\u00f6dinger equation for the quantum harmonic oscillator.
2. simplify computational procedures using the consequences of wavefunction orthogonality
3. explain the importance of kinetic and potential contributions to the total energy of a system
4. adjust a variational parameter to minimize the energy of a system
5. discuss the importance of the additivity of basis functions in achieving the best trial
Students should have at least two terms of calculus and a physics course, as well a solid introduction to quantum
mechanics. Students should be familiar with both the quantum particle-in-a-box and the quantum harmonic oscillator
problems. Additionally, they should understand the concepts of orthonormality and linear combinations of
wavefunctions. A rudimentary familiarity with Mathcad is required. A familiarity with the use of matrices and their
applications in quantum mechanics is useful.
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2. Knox, K., "Particle in the One-Dimensional Champagne Bottle," J. Chem. Ed.57, 626(1980).
3. Rioux, F., "Linear Variation Method in One Dimension (CS)", J. Chem. Ed.59, 773 (1982).
4. Knudson, S.K., "Applications of the Variation Method," J. Chem. Ed.74, 930 (1997).
5. Besalu, E. and Marti, J., "Exploring the Rayleigh-Ritz Variational Principle," J. Chem. Ed.75, 105 (1998).
6. Casaubon, J.I. and Doggett, G., "Variational Principle for a Particle in a Box," J. Chem. Ed.77, 1221 (2000).
7. Grubbs, W.T., "Variational Methods Applied to the Particle in the Box," J. Chem. Ed.78, 1557 (2001).
8. Raff, L.M., Principles of Physical Chemistry, Prentice Hall, Upper Saddle, NJ, 2001.
The Variational Method is one of the most important tools in computational quantum chemistry. The method itself is
simple, but the technique is often introduced using examples, such as the construction of molecular orbitals from
linear combinations of hydrogenic atomic orbitals, that obscure the basic principles of the technique with
complicated mathematical details. Several recent papers describe exercises that introduce the Variational Method
using simpler systems [1-7]. Reference , which provides a clever exercise where students find approximate
solutions to the particle-in-a-1d box problem is the only one that uses a Mathcad worksheet. Professor Grubb's
exercise demonstrates the basics of the Variational Method very clearly and efficiently. However, the project
presented here deals in greater depth with the construction of approximate wavefunctions using linear combinations of
basis functions, the backbone of Molecular Orbital (MO) Theory. In short, the students get hands-on experience with
all the important details of a MO calculation but in one dimension, where the wavefunctions are easy to graph and the
integrals are simple, before they are asked to solve more complicated problems using a computational chemistry
package like Spartan or Hyperchem.
In this exercise, students find approximate solutions to the Schr\u00f6dinger equation for the quantum harmonic oscillator using particle-in-a-1d box wavefunctions as a basis set. One of the most satisfying aspects of the exercise is that students can graph the one-dimensional basis functions and understand how these basis functions add together to produce the trial wavefunctions. Additionally, since the harmonic oscillator wavefunctions are known, the students can compare their trial wavefunctions and energies with actual ones. By comparison then, students can see the value and limitations of approximate methods of solving the Schr\u00f6dinger equation.
The Variation Theorem states that the energy obtained using a trial wavefunction will always be greater than or equal
to the true energy of the system. Therefore, the basic strategy of the Variational Method is to find the trial
wavefunction that results in the lowest possible energy.
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