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2: Approximation Methods

  • Page ID
    60510
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    Approximation methods can be used when exact solutions to the Schrödinger equation cannot be found. In applying quantum mechanics to 'real' chemical problems, one is usually faced with a Schrödinger differential equation for which, to date, no one has found an analytical solution. This is equally true for electronic and nuclear-motion problems. It has therefore proven essential to develop and efficiently implement mathematical methods which can provide approximate solutions to such eigenvalue equations. Two methods are widely used in this context- the variational method and perturbation theory. These tools, whose use permeates virtually all areas of theoretical chemistry, are briefly outlined here, and the details of perturbation theory are amplified in Appendix D

    • 2.1: The Variational Method
      Variational methods, in particular the linear variational method, are the most widely used approximation techniques in quantum chemistry. To implement such a method one needs to know the Hamiltonian whose energy levels are sought and one needs to construct a trial wavefunction in which some 'flexibility' exists (e.g., as in the linear variational method). This tool will be used to develop several of the most commonly used and powerful molecular orbital methods in chemistry.
    • 2.2: Perturbation Theory
      Perturbation theory is the second most widely used approximation method in quantum chemistry. It allows one to estimate the splittings and shifts in energy levels and changes in wavefunctions that occur when an external field (e.g., an electric or magnetic field or a field that is due to a surrounding set of 'ligands'- a crystal field) or a field arising when a previously-ignored term in the Hamiltonian is applied to a species whose 'unperturbed' states are known
    • 2.E: Approximation Methods (Exercises)
      Homework problems and select solutions to "Chapter 2: Approximation Methods" of Simons and Nichol's Quantum Mechanics in Chemistry Textmap.


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