Attribution Non-Commercial (BY-NC)

Als PDF, TXT **herunterladen** oder online auf Scribd lesen

9 Aufrufe

Attribution Non-Commercial (BY-NC)

Als PDF, TXT **herunterladen** oder online auf Scribd lesen

- nine theorems
- PX262 - Quantum Mechanics
- C. David Sherrill- An Introduction to Hartree-Fock Molecular Orbital Theory
- Theory of an Electro-cordic Field I PDF
- Spin Detector
- Collisions in Traps
- The time-independent Schrödinger eqn.Quantum Physics Lecture 11
- Atkins Heisenberg
- Chapter Two
- Particle in a One Dimensional Box
- Heart Centered Awareness
- PP-05-12
- How Atoms Work
- Chemistry Problem Set 2 Solutions
- Notes of Important Questions Answers of Fsc 11th Chemistry Chapter 5
- CHAPTER 3 FIX.docx
- IRP Test-1 (07!12!17) (JEE Mains) Code-A
- Lecture 6
- Chapter Six
- 0906.3206v1

Sie sind auf Seite 1von 8

We saw earlier that for the case of a free particle there was a general solution to the Schrödinger equation for that

particular system. This is often the case. Unfortunately, this means that mathematically there are often an infinite

number of solutions to the Schrödinger equation! Well mathematically many solutions may be possible, but

maybe physically they are not. We will call these extra criteria physical constraints on the acceptable

wavefunctions. The result from the physical interpretations of the wavefunction that we considered in the last

section:

2) Ψ ( x ) Ψ ( x ) is the probability density

∗

Since Ψ ( x ) Ψ ( x ) has a probabilistic interpretation, it must satisfy certain physical requirements. For example,

∗

an obvious one is the total probability for finding a particle somewhere must be unity.

∗

∫ Ψ (x ) Ψ (x )dx

allspace

= 1 (7.1)

The notation “all space” just means here that we integrate over all possible values of x. Wavefunctions that satisfy

the above equation are said to be normalised.

1

Even if the integral equals some constant other than 1, which we can denote by , we can multiply the

N2

wavefunction by N to normalise the wavefunction (make its integral over space equal one). Wavefunctions that can

be normalised are said to be normalized. Those that cannot are unacceptable. Often the wavefunction is such that

the integral diverges (get larger as x increases) and these functions will clearly not normalise. Consequently, we

find that a wavefunction MUST be finite everywhere (even if it is zero at some locations, that is okay)

These are both unacceptable because they manage to have two different values at the same position x, which

contradicts the Born interpretation. In addition, no gaps can appear in the wavefunction because the value of

Ψ ( x ) * Ψ ( x ) would be ill defined. In addition, the fact that a quantum object cannot have an infinite kinetic

energy requires that there must be a finite value for the wavefunction curvature.

A wavefunction is acceptable only if it (a) is continuous (b) has a continuous slope (c) is

single valued and (d) is finite.

These points become particularly important when there are so-called boundary conditions in place. These are

limitations or restrictions on a wavefunction that depend on a particular physical situation in question. The standing

wave considered earlier, like a plucked string, is a good example. A combination of the boundary conditions and

the restrictions imposed by the physical interpretation of the wavefunction is usually so restrictive that acceptable

solutions of the Schrödinger equation do not in general exist for arbitrary values of the energy E.

An example of this is a particle in a potential box with very high walls. The particle is assumed not to have enough

kinetic energy to escape the box. We don’t need to do the full mathematics, we just need to appreciate how the

quantization seeps in. At the walls of the box, we assume that each wavefunction must equal zero, otherwise the

quantum object can exist outside the confines of the box. We can see that only certain wavefunctions can obey

these restrictions and that they have very different wavelengths and hence energies: quantization!!!

What the allowed energies are we shall discover by solving the Schrödinger equation for a particular system and

selecting only those solutions that confirm to the restrictions. One such system is the hydrogen atom. This is the

simplest atomic system, possessing one electron and a central nucleus and what’s more it displays the important

features of more complicated atoms, namely that its electron can always be described by the four quantum

numbers n, l, ml and ms (whether the electron is excited or not).

In matter of fact, the hydrogen atom is one of the few instances where the Schrödinger equation can be

solved exactly. However, that does not mean it is easy to solve- without a background in pure

mathematics to degree level, forget it. Its solution draws on the work of some of the greatest

mathematicians of the 18th and 19th centuries. We don’t really need to solve it ourselves: we just need to

understand roughly what is going on.

First we must set up the Hamiltonian. The hydrogen atom contains a proton of charge +q, and an

electron of charge –q. The proton mass, m p , is roughly 1836 times greater than the mass of an electron

me . We must include BOTH in the Schrödinger equation. Also, a hydrogen atom is a three dimensional

quantum mechanical system, and therefore we have to use a three-dimensional version of the kinetic

energy operator

h2 ⎛ ∂2 ∂2 ∂2 ⎞ h2

− ⎜⎜ 2 + + ⎟

2 ⎟

= − ∇2 (7.2)

⎝ ∂x ∂y ∂z ⎠

2

2m 2m

∂2 ∂2 ∂2

where ∇ 2 = + + is known as the Laplacian operator. Finally, we must also

∂x 2 ∂y 2 ∂z 2

include the fact that there is a Coulombic attraction between the proton and electron, manifest as a

potential energy V (r ) , where r is the separation between the proton and the electron. From electrostatics

we have an expression for the Coulombic attraction

V (r ) =

(− q )(+ q ) = −

q2

(7.3)

4πε 0 r 4πε 0 r

where is the vacuum permittivity = 8.854 x 10-12 J-1 C2 m-1. The full Schrödinger equation for the hydrogen

atom is therefore

h2 h2 q2

Hˆ = − ∇p − ∇e − (7.4)

2 2

2m p 2me 4πε 0 r

⎛ 2 2 2 ⎞

⎜ − h ∇ p 2 − h ∇ e 2 − q ⎟ Ψ = EΨ

⎜ 2m 2me 4πε 0 r ⎟⎠

⎝ p

Doesn’t look like much, but the solution is very hard work and a person who can solve this is like a dog

that speaks Norwegian- very rare. However, we’ll let others do the work for us and concentrate only on

the solution.

A significant simplification is made by noting that since the proton is so much heavier than the electron,

its motion will be much smaller and hence we can place it at the centre of our co-ordinate system. If we

do this, we immediately see that the proton/electron system has spherical symmetry, because the

Coulomb potential only depends on the distance of separation between the electron and the proton.

Mathematicians exploit this fact by transforming the equation from Cartesian co-ordinates to spherical

ones. The three new co-ordinates are (r, θ and φ ).

The trick Schrödinger (who was a mathematical genius really) was to assume that the final wavefunction

was just a product of three separate wavefunctions that each depended on one of the variables

r, θ and φ .

Ψn ,l ,ml (r , θ , φ ) = Rn ,l ( r )Θ l , ml (θ )Φ ml (φ ) (7.5)

Then we find the hydrogen Schrödinger equation splits into three separate equations, one of which

depends on only the angle φ , another on the angle θ and finally one that just depends on r. The third

contains both θ and φ but if you first solve the equation with angle φ you can then solve this one. The key

point is that there are restrictions on the three individual wavefunctions, imposed by boundary conditions,

which results in the quantization of energy. By solving the Schrödinger three equations in turn we

actually retrieve the three quantum numbers n, l and ml . I will now explain where one of these

boundary conditions comes from.

Motion on a ring

Let us consider a particle confined to move on a ring. We assume that its wavefunction only depends on

the angle φ and that it possesses only the energy from its motion. We find that the appropriate

Schrödinger equation again has the general form

d2

Φ = −a 2 Φ (7.6)

dφ 2

where Φ is the wavefunction (which is a function of φ ) and a is just a constant. This equation is very

reminiscent of the one earlier for a free atom:

d2

2

Ψ = −a 2 Ψ

dx

but with Ψ replaced by Φ and x replaced by φ . The solution is therefore very familiar

Φ (φ ) = N m e aφ = N m e imφ (7.7)

However, there is one critical difference between this and the case of a free particle. For a free particle,

there was no boundary condition: this time there is. Think of the motion along co-ordinate as rather

like a wheel on a bicycle- after one complete rotation of the wheel (which is 2π radians in math speak),

the wheel is back to its original position. For our wavefunction, it means that Φ(φ + 2π ) must be

identical to Φ(φ ) . Applying this boundary condition to our proposed wavefunction

This can only be true if e im 2π = 1 and this turns can only be true if m2π is an integer multiple of 2π-

that is, m may only assume integer values.

If we simply re-label m as ml , we can see that the boundary condition is the reason why only

integer values of ml are allowed. We have just proved that ml can only have integer quantum

numbers- easy!! As you’ve probably guessed, we can find the remaining quantum numbers from the two

remaining Schrödinger equations. This is not something we will do this year!

Combining the two angular wavefunctions we obtain what is called a spherical harmonic:

Yl , ml (θ , φ ) = Θ l , ml (θ )Φ ml (φ ) (7.9)

Yl , ml (θ , φ ) is the eigenfunction for an angular momentum operator. This is not very surprising,

since the angular co-ordinates define they behaviour of both Θ l , ml (θ ) and Φ ml (φ ) . These

wavefunctions depend on two quantum numbers: l and ml. In fact, the eigenfunctions Yl , ml (θ , φ ) are

exactly the same as those for a particle trapped on the surface of a sphere (Prof Atkins does this

example in his textbook)! Below are the wavefunctions Y2, ml (θ , φ ) and yes you’re right these are just the

d-orbitals you’ve see a hundred times before!

Now, we must beware: the wavefunctions Yl , ml (θ , φ ) represent the angular part of the complete

hydrogen wavefunction, hence a hydrogen atom with n = 2 and l = 1 will not have precisely the same

appearance as one with n = 3, l = 1, because these have different principle quantum numbers n which we

discover by solving the last of our three equations for the wavefunction Rnl (r ) .

The solution, Rnl (r ) , of the radial equation is a function of r and also depends on the value of n and l.

We saw that we can force l to take only integer values if we have a suitable boundary condition. What

type of boundary condition can force n to take only integer values? Well, it has to do with the Coulombic

potential energy which we can model as a well with a proton at the centre:

This kind of boundary condition is very common, and is idealised in the so-called particle in a box

model we saw at the beginning of the lecture. Basically, think back to our standing wave analogy: the

walls of the potential are like the fixed points of the string. They set the boundary condition that forces

only discrete values of energy to be supported by the Coulomb potential. The different discrete values are

labelled by the quantum number n.

What do these radial wavefunctions “look” like? Well, they depend on r and are parameterised by n

and l (that means that there appearance is affected by the values these quantum numbers take).

Now before we finish I have to mention a little more mathematics but it is important: true solutions

(eigenfunctions) of the must be orthogonal to one another. This means if we take two wavefunctions,

multiply them together and integrate over all space then the result of the integration is a big fat zero. All

the radial wavefunctions with the same l are orthogonal, as are all angular momentum wavefunctions with

the same n and this means that if we leave the electrons in an atom alone, they will happily stay with their

original wavefunctions and will not go hopping about from one wavefunction to the next unless an

external force is applied. When we find two are more wavefunctions with the same

energy (degenerate) that are not orthogonal, we must combine them together to

form a true orthogonal pair: more on this in the next lecture.

Note that none of this has explained the fourth quantum number ms. As the Hamiltonian we used doesn’t

include spin, it is perhaps not surprising that we get no information on this quantum number. A slightly

more complex equation- the Dirac equation – does include spin but it is not as easy to use as the

Schrödinger equation. We will revisit this next year.

Good. Now we see that solving the hydrogen provides the angular and radial wavefunctions for the

hydrogen system. However, hydrogen is not a typical atom: for example, we know that in many-electron

atoms states with the same n but different l are non-degenerate. It is natural to ask:

• The three quantum numbers: n, the principle quantum number; l , the orbital angular

momentum; and ml the magnetic orbital quantum number are found by solving the

Schrödinger equation for the hydrogen atom.

• The solution of the hydrogen atom is most easily found using spherical co-ordinates to

describe the electron. When this is done, the equation is split into three separate equations, two

of which are the same as for a particle moving on the surface of a sphere while the third depends

only on the radial co-ordinate.

• The angular part of the wavefunction is described by special wavefunctions called spherical

harmonics which correspond to the picture of “orbitals” chemists use.

• The radial wavefunctions are different for identical l but different n and is the reason for rows

in the periodic table.

• The hydrogen wavefunctions are orthogonal, ensuring they are unique mathematical solutions.

- nine theoremsHochgeladen vonsam iam / Salvatore Gerard Micheal
- PX262 - Quantum MechanicsHochgeladen vonRebecca Rumsey
- C. David Sherrill- An Introduction to Hartree-Fock Molecular Orbital TheoryHochgeladen vonElectro_Lite
- Theory of an Electro-cordic Field I PDFHochgeladen vonrwayte
- Spin DetectorHochgeladen vonmkrinker1296
- Collisions in TrapsHochgeladen vonVARUN SHARMA
- The time-independent Schrödinger eqn.Quantum Physics Lecture 11Hochgeladen vonkorna2
- Atkins HeisenbergHochgeladen vonThejas C S
- Chapter TwoHochgeladen vonProf. Dr. Hassan N. Al-Obaidi
- Particle in a One Dimensional BoxHochgeladen vonAgnivesh Sharma
- Heart Centered AwarenessHochgeladen vonthewhiteeye
- PP-05-12Hochgeladen vonAnonymous 0U9j6BLllB
- How Atoms WorkHochgeladen vonapi-3709951
- Chemistry Problem Set 2 SolutionsHochgeladen vonhydrazine23
- Notes of Important Questions Answers of Fsc 11th Chemistry Chapter 5Hochgeladen vonshahrukh
- CHAPTER 3 FIX.docxHochgeladen vonBaiq Arum Kusuma
- IRP Test-1 (07!12!17) (JEE Mains) Code-AHochgeladen vonvejoshi21699
- Lecture 6Hochgeladen vonAjay Kaladharan
- Chapter SixHochgeladen vonalexandru_bratu_6
- 0906.3206v1Hochgeladen voncocoaramirez
- Shulman TimeHochgeladen vonNoDual
- Special Function GuideHochgeladen vonBuddhadev Bhattacharya
- Chap1x-327Hochgeladen vonFrancisco Carlos Marques da Silva
- Exercise Sheet -5Hochgeladen vonHardeepSingh
- electron configurations and orbital diagramsHochgeladen vonapi-182809945
- Solution-Homework-3-16.pdfHochgeladen vonSumantri Hatmoko
- J. Weiß et al- Saddle-node bifurcations in the spectrum of HOClHochgeladen vonImasmz
- Color Atlas of Biochemistry (Thieme 2005).pdfHochgeladen vons_fawzyhafez
- 74952 SpecificationHochgeladen vonYan Ho Yeung
- whatBleep.pdfHochgeladen vonRajesh Kumar

- 2006-7 Module 113 - lecture 8Hochgeladen vonapi-19928045
- 2006-7 Module 113 - lecture 6Hochgeladen vonapi-19928045
- 2006-7 Module 113 - lecture 5Hochgeladen vonapi-19928045
- 2006-7 Module 113 - lecture 4Hochgeladen vonapi-19928045
- 2006-7 Module 113 - lecture 3Hochgeladen vonapi-19928045
- 2006-7 Module 113 - lecture 2Hochgeladen vonapi-19928045
- 2006-7 Module 113 - lecture 1Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 8Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 7Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 6Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 5Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 4Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 3Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 2Hochgeladen vonapi-19928045
- 2006-7 quantum theory slides lecture 1Hochgeladen vonapi-19928045

- Product ViewHochgeladen vonSushant Pilankar
- Modem Usb Gprs Data Sheet itegnoHochgeladen vonFrancisc Fery
- 111_IsolatorHochgeladen vonsunilmaurya22
- District Cooling SyHochgeladen vonAnand Nambiar
- Oracle RmanHochgeladen vonFantasytrend
- CPR RequirementsHochgeladen vonobietobi
- NOypiel.pdfHochgeladen vonbiofisicas
- Yuriyandinna.com-The Ten QuestionsHochgeladen vonmotaheri
- Wisdom to ProsperHochgeladen vonEwolrAm ZEuqram
- Strength of MaterialsHochgeladen vonEkajara Josh
- HK G36 Assault Rifle ManualHochgeladen vonGasMaskBob
- Slides Aula20Hochgeladen vonJanainaFernandes
- Vol 55 4 Handling and Transportation of Broilers WelfareHochgeladen vonSpellcaster
- Ind Article 3 EchrHochgeladen vonApollyon
- BayesBookWebHochgeladen vonSheldon Cooper
- Safety Profile and Effect on Libido of a Combined Bryophyllum Pinnatum, Moringa Oleifera and Vitamin C Phytotherapeutic Agent - Golden Leash Pet ProductsHochgeladen vonMoringa Customer Care
- Openfoam for windowsHochgeladen vonRajat Ravikumar
- Gary a. Olson Philosophy, Rhetoric, Literary Criticism Interviews 1994Hochgeladen vonhoraciotoledano
- Richards 2011Hochgeladen vonVarriz Gella
- BARNapxC_p1584-1594Hochgeladen vondraykid
- Automatic Self-Climbing Formwork PeriHochgeladen vonSivaram Kottali
- Pedramt Hw9 CodeHochgeladen vonPedram To
- Coupled Fluid Flow and Radiation Modeling of a Small Parti̇cle Solar Recei̇verHochgeladen vongldn1gldn
- Lab 9.3.3 Troubleshooting Physical ConnectivityHochgeladen vononlycisco.tk
- Hi5100601CMEN5Hochgeladen vonAravindhan
- UL325_Presentation_Rev5.pdfHochgeladen vonHJ
- Decuscope_Vol10_1971Hochgeladen vonkgrhoads
- Lesson 21 Science Body parts of Animals that live on landHochgeladen vonMaricel Cebrero Santiago
- Re Envisioning SocialismHochgeladen vonapi-3740264
- A Stay at Home SCAMPI AppraisalHochgeladen vonohmega