Lecture 20A: Bohrs model of the atom

A brief history of atomic structure Rutherfords scattering experiment The problems with Rutherfords model Bohrs postulates Bohrs 1st postulate A closer look Developing Bohrs model Optical spectroscopy Two types of spectroscopy Spectroscopy as an analytical tool The spectrum of Hydrogen The Rydberg-Ritz equation
PHYS2040 Lecture 20A Bohrs model of the atom PHYS 2040 Quantum Updated:Physics 19/5/2008 8:42 PM

A brief history of atomic structure

One of the first models of the structure of the atom (beyond just being the smallest possible piece of some material) was known as Thompsons plum-pudding model. It relied upon a few pieces of knowledge that were emerging from experiments at the time, namely: Atoms contain particles with negative charge than can come out (i.e., electrons) as found in the photoelectric effect. Overall, an atom is neutral, so therefore there must also be a compensating amount of positive charge in the atom. The mass of an atom is ~1800 times that of an electron, therefore an atom must be mostly positive charge by mass (not by charge though, since the total charge must be neutral see 2). If you take these three observations, the simplest model you can generate is the plum-pudding model, where the atom is a ball of mostly positive charge, with small negatively charged particles embedded inside it. ~1

1.

2.

3.

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Rutherfords scattering experiment

In around 1910, a New Zealander Ernest Rutherford and colleagues were looking at the scattering of alpha particles (helium nuclei with 2 protons and 2 neutrons therefore it has charge 2+) from a very thin leaf of gold foil. Foil is relatively homogeneous and has no free charge, so s should go roughly straight through

The expectation was that almost all of the -particles should be transmitted, because in the plum-pudding model, a material is very homogeneous and there is no free charge to backscatter the positively charged -particles. Thompsons model predicted that ~1 in 103500 -particles would be backscattered.
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Rutherfords scattering experiment

Rutherfords result was quite surprising. He found that significantly more -particles were reflected, approximately 1 in 104. It was the most incredible event that ever happened to me in my life. It was as incredible as if you fired a 15-inch artillery shell at a piece of tissue paper, and it came back and hit you." Ernst Rutherford.

This can only be explained if the relatively massive positive charge and relatively massless negative charge are separate in the atom. Then, the enhanced backscattering is due to the -particles experiencing Coulomb repulsion off the positive nuclei. In this model, the nucleus is small, and the rest of the volume of the atom is made up of a cloud of electrons orbiting the nucleus.

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Rutherfords model of the atom

Based on his experiments, Rutherford arrived at a new model for the atom, based on the idea that the nucleus and the electrons are separate, distinguishable objects.

The key idea behind Rutherfords model is that an electron in an atom moves in a circular orbit about the nucleus under the influence of the Coulomb attraction between the electron and the nucleus, obeying the laws of classical mechanics.

Rutherfords model is basically this picture of electrons in planetary orbits around a nucleus that we often see drawn inside/outside science.

Despite the fact that Rutherfords model is an improvement on Thompsons plum-pudding model, it also has its problems

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The problems with the Rutherford model

The problems with the Rutherford model are actually quite simple The negatively charged electron should be drawn slowly in towards the positive nucleus, continuously emitting energy until it crashes into the nucleus (and eventually ending up as the plum pudding model again). And in the process it should emit radiation of frequency f 1/r3/2, which should increase continuously as the electron spirals inwards, but experimentally the emission spectrum for hydrogen is discrete (as we will see later).

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Bohrs Postulates

In 1913, Bohr developed a new model. It is still based on Rutherfords idea that the electron follows a circular orbit due to Coulomb attraction between the electron and the nucleus, but Bohr added on three simple postulates to avoid the problems with Rutherfords model of the atom. These postulates are: Instead of the infinity of orbits allowed classically, it is only possible for an electron to move in an orbit for which its orbital angular momentum L is an integer multiple of h. In other words, L = nh where n = 1, 2, 3, is an integer. We typically call n a quantum number (we will see more of this in the coming weeks). Despite the fact that it is constantly accelerating, an electron moving in such an orbit does not radiate electromagnetic energy. Thus its total energy E remains constant, unless it changes to another orbit. Electromagnetic radiation is emitted if an electron, initially moving in an orbit of total energy Ei, discontinuously changes its motion so that it moves in an orbit of total energy Ef. The frequency of the emitted radiation f is equal to (Ei Ef)/h. Postulate 1 actually has some hidden meaning in it, lets take a closer look at it before moving on
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1.

2.

3.

Bohrs 1st postulate A closer look

1. Instead of the infinity of orbits allowed classically, it is only possible for an electron to move in an orbit for which its orbital angular momentum L is an integer multiple of h. In other words, L = nh where n = 1, 2, 3, is an integer If we consider that L = mvr = nh, then we can rearrange to obtain the radius r = nh/mv The circumference or length l of an orbit is given by l = 2r = 2nh/mv = nh/mv Remembering back to the de Broglie relation: p = mv = h/, then = h/mv And if we feed this back into our earlier result l = nh/mv = n, in other words, the number of electron wavelengths around an orbit must be an integer. This, as we saw earlier, was part of the motivation for de Broglie in establishing his relations. n=3 These sorts of logical loops are very useful in science, they often reassure you that you are on the right track. Also, as a student, they give you more than one way to remember useful facts, good back-up for exams.
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Developing Bohrs Model

So now lets start with Rutherfords model work our way through Bohrs postulates, and see if we can calculate what the allowed radii of the electron orbits will be, use this to obtain the corresponding electron energies, and then try to calculate the expected atomic absorption/emission spectra. We can then compare this to experimental results. Were going to start here with the simplest case a hydrogen atom - with one proton and one electron. It turns out Bohrs model starts to fail as we make much larger atoms, but that doesnt stop it from being a good place to start. Rutherfords model: An electron in an atom moves in a circular orbit about the nucleus under the influence of the Coulomb attraction between the electron and the nucleus, obeying the laws of classical mechanics.

This means that the centripetal force on the electron that makes it take a circular path will be provided by the Coulomb force acting between the negative electron (e) and the positive nucleus (+Ze, where Z is the atomic number), therefore:

mv 2 Ze 2 = r 4 0 r 2
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(19.1)

Developing Bohrs Model

If we now consider postulate 1 again:

L = mvr = nh

(19.2) (19.3)

v=

nh mr

and then substitute Eqn. 19.3 back into Eqn. 19.1, we find:

m nh n 2h 2 Ze 2 = = 3 r mr mr 4 0 r 2
cross-multiply to get:

(19.4)

Ze 2 mr 3 = 4 0 n 2 h 2 r 2

(19.5)

and then isolate r:

4 0 n 2 h 2 0h2 2 = r= n 2 2 mZe mZe

(19.6)

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Developing Bohrs Model

We can now calculate the energy E as the kinetic energy K plus potential energy V:

1 2 Ze 2 E = K + V = mv 2 4 0 r
if we now go back to Eqn. 19.1 and multiply both sides by r/2, then:

(19.7)

mv 2 Ze 2 = 2 8 0 r
substituting 19.8 into 19.7:

(19.8)

Ze 2 Ze 2 Ze 2 E= = 8 0 r 4 0 r 8 0 r Ze 2 mZe 2 E= 8 0 0 h 2 n 2

(19.9)

and then substituting in r:

(19.10)

mZ 2 e 4 = 2 8 0 h 2 n 2
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(19.11)

Collecting our results

We now have expressions for the allowed radii and corresponding energy levels:

0 h 2 2 a0 2 rn = n = n 2 mZe Z
where:

(19.6)

Z 2 E0 mZ 2 e 4 En = = 2 2 2 2 n 8 0 h n

(19.11)

a0 = 0h2/me2 = 0.53 is called the Bohr radius E0 = e2/80r0 = me4/80h2 = 13.6eV is called the Rydberg energy

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The fine-structure constant

It is also interesting to calculate the electrons speed as it travels around an orbit. We can do this by going back to:

v=

nh mr

(19.3)

And then substitute in appropriate values for n and rn (from Eqn. 19.6).

For hydrogen in the ground state, n = 1, Z = 1 and r = a0, and if you use these values, you get v1 = 2.18 106 ms1, which is 0.73% of the speed of light, justifying the fact that we havent used relativity for this problem, but indicative of the fact that if r << a0 we might need to do so, as you find for heavy nuclei (Z large) where relativistic corrections are important. The ratio of v1 to c for the Hydrogen atom (Z = 1) is actually a very important constant in physics called the fine structure constant . It is given by:

h v1 e2 1 = = = c mca0 4 0 hc 137
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(19.11)

Emission and Absorption

And using postulate 3, we can now calculate the frequency/wavelength of radiation emitted by an electron going from level n to level m as (we will set Z = 1 from here onwards):

En Em me 4 1 1 = f = 2 3 2 2 h m 8 0 h n me 4 1 1 = 2 3 2 2 m 8 0 h c n 1
1 1 = R 2 2 m n 1
where: R = me4/802h3c = 1.097373 107 m1 is called Rydbergs constant

(19.12)

(19.13)

(19.14)

Fantastic! We now have something observable that we can use to test Bohrs model. We can take a gas of hydrogen atoms, and see what wavelengths of photons are emitted/absorbed, and these should hopefully obey Eqn. 19.14. So lets do this
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Optical spectroscopy

A spectrometer basically uses Newtons discovery that a glass prism can be used to disperse light based on its wavelength (you can also use a diffraction grating to achieve the same effect). You can then measure the spectral content of the light, in other words, its intensity as a function of wavelength.

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Two types of spectroscopy

The two main types of spectroscopy are emission and absorption spectroscopy. In emission spectroscopy, a gas of excited atoms emit photons at frequencies corresponding to transitions to lower electronic energy level n. In absorption spectroscopy, a gas absorbs photons of frequencies corresponding to transitions to higher electronic energy level n.

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Spectroscopy as an analytical tool

Different atoms have different electronic energy level structures, and thus different emission and absorption spectra, and hence this can be used as a tool to identify the composition of gases. This is particularly important in astronomy!

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The spectrum of Hydrogen

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The spectrum of Hydrogen

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The Rydberg-Ritz equation

The wavelengths of the spectral lines in hydrogen can be fitted by the following equation:

1 1 = R 2 2 m n 1

(19.15)

which is known as the Rydberg-Ritz equation (and is the same equation as Eqn 19.14). Before Bohrs model no physical explanation could be given for this relationship, it simply worked.

The measured R was 10967757.6 1.2 m1 and the Bohrs model calculation of R, corrected for the finite mass of the hydrogen atom, gives R = 10968100 m1. These values agree to within 3 parts in 100,000! This gave impressive confirmation of the Bohr model, and earned Bohr the Nobel prize in Physics in 1922.
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Summary

The earliest model for the structure of the atom was provided by J.J. Thompson, and was called the plum-pudding model. It consists of a ball of positive charge, with negatively charged electrons embedded in it. It relies on the knowledge that atoms can eject negatively charged electrons, atoms are generally neutral and have a mass roughly 1800 times that of an electron. Rutherfords work scattering alpha-particles (He2+ ions) off thin gold films showed far more backscattering than can be explained by the plum-pudding model. His conclusion was that a cloud of electrons orbit a very small positive nucleus, but faced a significant problem in such a model, the electron should spiral back in towards the nucleus. Bohr aimed to improve this model by adding three postulates that the angular momentum of electron orbits is quantised in integer multiples of h, an electron in a fixed orbit doesnt radiate energy, and an electron changing orbits emits/absorbs a photon with a frequency corresponding to the energy difference between levels. Bohrs model does an excellent job of predicting the emission/absorption spectra of simple one-electron atoms such as hydrogen (and other group I elements if you correct for finite mass), but fails for larger, multi-electron atoms. The relationship between the emission/absorption wavelength and the transitions is given by the Rydberg-Ritz equation.

= Brooks/Cole - Thomson

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