Lecture Thursday 14.

January 2010
Topics: Quantum Mechanics Bound states discrete spectrum Binding of Molecules, Crystals Hydrogen Molecule Ion LCAO generally will be used later All systems with equillibrium must have harmonic motion as lowest energy region, see Taylor expansion, quadratic term Where does the minimum come from? Eigenmodes of harmonic systems Comment:
(Text-Presentation SolidState-HarmOsc-2008.pdf )

This is an edited version (Monday January 18th), with some comments added after the lecture

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Crystals as huge molecules: To use this metaphor, we need to know how the molecules are kept together. The capture of the drawing shows a discussion of the simplest molecule - H2 molecule which consists of two protons and ONE ELECTRON. Such ionized hydrogen molecule exists in Nature and is stable
+

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from our PDF -text page 55 The potentials shown might be representative for some ionic type solids, but do not explain the most fundamental type of interactions, as they appear in simplest molecules. In most cases, the attractive component is the covalent binding, i.e. sharing of one electron state between two atomic centers; + in quantum-mechanics model binding of an electron to two atoms as exemplified in the - H2 molecule discussion on the previous page

from our PDF -text page 55

Understanding of the stability of solids requires quantum mechanics. The picture from our text is thus somewhat misleading
van der Waals interaction is a model of interatomic interaction, justifiable only on the basis of Quantum Mechanics

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What did we say: Hooke's law is very old; Newton times; oscillation is a basic type of motion; Whenever there is equillibrium, there must be a minimum in potential energy Taylor series contains quadratic term; Hooke's law: Quadratic form of potential energy
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The solution is assumed to be a linear combination of the two known solutions One with the first binding potential present Another with only the second potential present It is not essential, but it gets much simpler If we can assume that The method gets much simpler to erite and understand in DIRAC NOTATION

The method of expansion of a function (unknown) As a sum of 'basis functions' This method is a basis of e.g. Fourier series In quantum mechanics this is a very usual method It appears in several stages of Quant. Mech presentations. e.g. in Perturbation theory Or e.g. in presentation of probability amplitudes The form we discuss here is a simplest version of

LCAO Linear Combination of Atomic Orbitals

which originates from Quantum Chemistry

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On previous board copy to the right -> We set up 2 equations

They can be rewritten as a matrix equation This is always the case (or often!) BASIS OF MATRIX MECHANICS Or Matrix Quantum Mechanics Basis of many approximative methods

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These 2 equations obtained above can be written as a matrix equation

Solving this matrix equation is sometimes called DIAGONALIZATION of the matrix On the left hand side

Matrix DIAGONALIZATION of this type of matrix Is an elementary problem

It is easy to obtain; will be used later Here we simply check that these are really solutions NOTE THE EIGENVECTORS Which give the solutions for the above Unknown coefficients c1, c2

NOTE THE EIGENVALUES give this approximate solutions for the the energies of the electron as the distance between the two protons is changing

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Understanding of the electron bound state energies ( 2 lowest states) of the HYDROGEN MOLECULE ION simplest molecule possible IN THE LECTURE -

see also extra comments next page

1/R is the R-dependence of the proton-proton repulsion

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Understanding of the electron bound state energies Of HYDROGEN MOLECULE ION - simplest molecule possible Numerically Exact solutions can by found by several methods The sketched LCAO could have a certain validity only for large R The essential features are however correct The states of the electron behave basically as told here The discussion here gives us the dependence; The values for SMALL R->0 can be estimeted from another consideration As R->0, the two protons form a sort of nucleus of He (we are missing the 2 neutrons to form the real He nucleus But we know that the states in hydrogen-like atoms 'scale' as Z2 Task: sketch the levels of HYDROGEN MOLECULE ION Combining the values from this discussion with the shape argument

Additional Notes

In chemistry, we hear about

Ionic bonding Covalent Bonding Hydrogen Bonds (only one electron in a somewhat special orbital) as in hydrogen molecule; two electrons in an orbital

From the point of this discussion, they are all of them the same type caused by quantum bound states of electrons; But most different is the hydrogen bond, very important in the structure of water TASK: Look at the chemistry definitions, consult various textbooks on our topics
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Harmonic vibrations for systems coupled by 'springs', eigenmodes, Lagrange Function, Newton equations

Lagrange Equation Energies E=T+V L = T V Newton Equations Forces

Newton follows from Lagrange (mathematical)
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Eigenmodes text on harmonic oscillators classical mechanics Which we went through (read the text)

Eigenmodes Instead textbooks look for DISPERSION RELATIONS It is search of eigenmodes .... The text on eigenmodes is also included in our text collection

NEXT TIME: RELATIONS

LOOKING FOR THE DISPERSION

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