CH4 ATOMIC STRUCTURE

Around late 19th century, most scientists accepted the idea that the chemical elements consist of atoms, but they knew almost nothing about the atoms themselves. One clue was the discovery that all atoms contain electrons. (J.J. Thomson in 1897 ). Since electrons carry negative charges whereas atoms are neutral, positively charged matter of some kind must be present in atoms. But what kind? Thomsons model of atom: British physicist J.J. Thomson (1898) proposed the first model of an atom: J.J.Thomsons atom consists of a spherical cloud of positive charge, roughly 10-10 m in diameter, in which the smaller negative electrons are embedded, just like negative charged "plums" that are surrounded by positive-charged "pudding".

Then positive charges exactly balances the negative charge, so the atom as a whole has no net charge. But the real atom turned out to be quite different.

Rutherfords model of atom: As a student of Thomson, E. Rutherford set up an experiment in 1911 to prove the model. Fast -particles emitted by certain radioactive elements were used as probes. ( particles are helium atoms that have lost two electrons, leaving them with a charge of +2e). The beam of -particles was directed at a thin gold foil. A zinc sulfide screen, which gives off a visible flash of light when struck by an -particle, was set around the foil with a microscope to see the flashes.

Since according the Thomsons model, electric charge inside the atom is assumed to be uniformly distributed through its volume, it was expected that the -particles would go right through the foil with hardly any deflection. (Electric field inside the atom should be quite small and electric force on an be quite weak). , so momentum considerations show that the -particle can be scattered only a very small amount by its interaction with the electrons. that enters the atom should

What Rutherford actually found was that most of the -particles indeed were not deviated much, but a few were scattered through very large angles. Some were even scattered in the backward direction The only way to explain the result was to picture the atom as beeing composed of a tiny nucleus in which its positive charge and nearly all its mass are concentrated with electrons some distance away. An atom is largely empty space, thus it is easy to see why most -particles go right through a thin foil. However when an -particle comes near a nucleus, the intense electric field there scatters it through a large angle.

Rutherford Scattering Formula Rutherford model of the atom was accepted because he was able to arrive at a formula to describe the scattering of -particles by thin foils on the basis of this model that agreed with the experiment. He assumed that -particle and the nucleus are both small enough to be considered as point masses and charges that the repulsive electric force between -particle and nucleus is the only force and the nucleus is so massive that it does not move during the interaction . The geometric relationships in Rutherfords formula are given in the figure below. Since , where is the instantaneous separation between particle (projectile) and target nucleus, the -particles path is a hyperbola with

: number of -particles per unit area that reach the screen at a scattering angle of . : total number of -particles that reach the screen n : number of atoms per unit volume in the foil. Z : atomic number of the foil atoms (It is the number of protons in the atom). r : the distance of the screen from the foil. KE : kinetic energy of the -particles. t : foil thickness b : impact parameter; the minimum distance to which -particle would approach the target nucleus if there were no force between them. Predictions of this equation agreed with the measurements which supported the hypothesis of the nuclear atom.

Nuclear Dimensions In deriving the formula , Rutherford assumed that -particle and the nucleus are both small compared with the minimum distance rmin to which incident -particles approach the nucleus before being deflected away. Therefore, Rutherford scattering gives us a way to find an upper limit to nuclear dimension: None of the -particles penetrate inside the nucleus; that is, for all trajectories the distance r from -particle to the nuclear center is always greater than R. The minimum of r occurs for the case of head-on collision: Let us first estimate R : r=rminwhen the -particle approaches the nucleus headon, which will be followed by a 1800 scattering. At the instant of the closest approach,

If given that (the max KE found in -particles of natural origin)

then

F.ex., for gold foil atomic number Z=79 so that

The measured value of radius gold nucleus is

/5.

ELECTRON ORBITS

Planetary Model of the Atom

In Rutherford model, atom is composed of a tiny nucleus in which its positive charge and nearly all its mass are concentrated with electrons some distance away. In this model, electrons can not be stationary, since electric force pulls them to the nucleus and against this force there is nothing to keep them in place. However, if electrons are in motion, then dynamically stable orbits like those of the planets around the sun are possible.

Let us consider the simplest atom, H-atom, that has only one electron and one proton . Let us look at the classical dynamics of H-atom . For simplicity we assume the circular orbit.

Electron orbits in circular orbit under Coulomb attraction

e2 4
2 0r

me aR ,
: orbital acceleration

e : magnitude of the charge of the electron

Then the electron velocity is related to its orbit radius r:

Total energy of the H-atom;

Substituting

gives

Note that E<0. This holds for every atomic electron and reflects that fact that it is bound to nucleus.

EX1: Experiments shows that the energy required to separate a H-atom into a proton and an electron, is E=13.6 eV. Find the orbital radius and velocity of the electron in an H-atom From ,

For velocity, we have

Note that

, we can ignore special relativity when considering H-atom.

The Failure of Classical Physics Rutherford model of the atom together with the Newtons law of motion and Coulombs law of electric force are in agreement with the experimental observations that atoms are stable. However, it is not in accord with EM-theory, which predicts that accelerated electrons radiate energy in form of electromagnetic waves. Then an electron following a curved path is accelerated and therefore should continuously lose energy, spiraling into the nucleus in a fraction of a second ! But atoms do not collapse ! This contradiction illustrates that the laws of physics that are valid in the macro-world do not always hold true in the micro-world of the atoms. Although to think of the atoms in terms of Rutherfords model is correct, the dynamics of the atomic electrons requires a non-classical approach: A successful theory of the atom must account for the atomic stability.

ATOMIC SPECTRA Another important aspect of the atom that finds no explanation in classical physics is the existence of spectral lines . When an atomic gas is suitably exited (usually by passing an electric current through it) it gives off light. The emitted light is then passed through a prism which seperates it into its constituent wavelengths . The result is a spectrum which contains certain specific wavelengths only. A spectrum of this sort is called a line spectrum. An idealized arrangement for observing such atomic spectra is shown in the figure.

The figure shows the emission line spectra of several elements, together with one from light bulb. Every element displays a unique line spectrum : the emission spectrum is a fingerprint of the element/molecule that generates it. Therefore, spectroscopy is a useful tool for analyzing the composition of an unknown substance.

Spectral Series In 1885, J.J. Balmer discovered that the wavelengths in the visible part of the hydrogen spectrum showed regularity. These regular sets are called spectral series. The figure below shows the Balmer series.

The line with the longest is specified , the next with is specified , and so on. Balmers formula for the wavelengths of this series (which were obtained by trial and error) is

where

The line corresponds to n=3, the line to n=4, and so on. The series limit corresponds to n= , so that it occurs at a , in agreement with experiment. Balmer series contains s in the visible portion of the H-spectrum. The spectral lines of H in the ultraviolet and infrared regions fall into several other series.

In the ultraviolet the Lyman series contains the

given by the formula

In the infrared,

These observed regularities in the H-spectrum, together with similar regularities in the spectra of more complex elements, pose a definitive test for any theory of atomic structure.

The Bohr Atom Niels Bohr, a Danish physicist had studied in Rutherfords laboratory for several months in 1912 and he was convinced that Rutherfords planetary model of the atom had validity; but in order to make it work, he felt that the newly developing quantum theory would somehow have to be incorporated in it. For this , Bohr made some postulates: 1. Electrons move about the nucleus in circular orbits (known as stationary states) under the influence of the Coulomb attraction between the electrons and the nucleus, obeying the laws of classical mechanics. 2. Despite the fact that it is constantly accelerating, an electron moving in such an allowed orbit does not radiate electromagnetic energy. Thus, its total energy E remains constant. 3. Electromagnetic radiation is 1. emitted if an electron, initially 2. 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 to is equal

+ Bohr found that his theory would be in accord with the Balmer formula if he assumed that electrons angular momentum is quantized

which leads to the quantization of orbits. Bohr model was successful at explaining why atoms emit line spectra , but it was largely of an ad hoc nature. Assumptions were made so that the theory would agree with the experiment. However, Bohr could give no reason why the orbits (and the angular momentum ) were quantized. Finally , 10 years later, a reason was proposed by de Broglie: He proposed that material particles, such as, electrons, have a wave nature. But Bohr himself used a different approach. Let us consider the wave behavior of an electron in an orbit around the Hatom: De Broglie wavelength of the electron is

Note that this wavelength is exactly the same as the circumference of the electron orbit :

Note that

!!!

Thus, the orbit of the electron in a H-atom corresponds to one complete electron wave joined on itself !

If we consider the vibrations of a wire loop , we find that their wavelenghts always fit an integral number of times into the loops circumference . If a fractional number of wavelengths is placed around a loop, as in the figure below, destructive interference occurs , and the vibration will die rapidly.

Thus, condition for orbit stability can be expressed as

2 rn n

, n=1,2,3,

where rn represents the radius of the orbit that contain n wavelengths. Integer n is called the quantum number of the orbit. To find orbital radii in Bohr atom,

The radius of the innermost orbit is customarily called the Bohr radius of the Hatom and is denoted by the symbol

Then, the other radii can be written as

ENERGY LEVELS AND SPECTRA Total energy of the H-atom was calculated as

Sunstituting

, we find

The energies specified by this equation are called the energy levels of the H-atom and are plotted in figure below:

Note that: Energy levels are all negative, which indicates that the electrons are bounded to the H-atom. The lowest energy level is called the ground state of the atom, and the higher levels are called excited states. As n increases approaches to zero. In the limit of . Then, the electron is no longer bound to the nucleus to form an atom. When E>0, electron is free and its energy is no longer quantized. ( Such a combination does not constitude an atom, of course) The work needed to remove an electron from an atom in its ground state is called its ionization energy, . It is equal to . For H-atom, it is 13.6 eV.

Origin of Line Spectra Is there any experimental test of the Bohr model ? Atoms exhibit line spectra in both absorption and emission. Do such spectra follow from this model? In Bohr model, there are discrete energy levels in H-atom. When an electron in an excited state drops to a lower state, the lost energy is emitted as a single photon . If the quantum number of the initial state is and the final one is , then the photon will have the energy given by

where

is the frequency of the emitted photon. Writing energies explicitly as,

(Note that

we find

Since

Thus, radiation emitted by excited H-atoms should contain certain wavelengths only. These wavelengths fall into definite sequences. The first few series are:

These sequences are identical in form with the empirical spectral series discussed earlier; provided that

To see this, let us calculate

which is indeed the same as the

R.

Bohr model of H-atom is therefore in accord with the spectral data.

CORRESPONDANCE PRINCIPLE In our study of relativity, we saw that Newtonian mechanics is a special case of relativistic mechanics and is applicable only for speeds less than c. Similarly, predictions of quantum physics agrees with those of classical physics in the region of sizes where classical theory is known to hold. This principle, first set forth by Bohr, is called the correspondence principle. The classical sizes for length, mass, and time are on the order of milimeters, grams, and seconds, and typically involve very large quantum numbers, as we have seen when we calculated the quantum number n for a H-atom with radius of 0.01 mm. (Ex.4.3) Therefore we may state the correspondence principle symbolically as

We will show how the Bohr theory satisfies the correspondence principle. The Classical Result Consider an electron orbiting in the H-atom with n>10000. For such large values of n, the energy differences between adjacent levels approach zero; therefore, the levels are nearly continuous. Consequently, the classical model is reasonably accurate in describing the system for large values of n. According to classical em theory , an electron moving in a circular orbit radiates em waves whose frequencies f are equal to its frequency of revolution :

For nth stable orbit with radius

the frequency of revolution is

Large Quantum Numbers: Let us now consider an electronic transition between two adjacent orbits corresponding to very large quantum numbers, which would correspond to a system that sits in the classical physics regime. The energy emitted during such a transition is found easily from the Bohr theory to be

Now if n is much greater than unity,

and so the energy released is

The frequency of the radiation released is

That is, the frequency of emitted radiation in the classical limit is simply equal to the frequency of rotation of the electron around the nucleus. This is the classical limit that we expect from the correspondence principle.

NUCLEAR MOTION

Thus far it was assumed that the hydrogen nucleus (a proton) was fixed, and that the electron in the hydrogen atom rotated around the fixed nucleus. In reality, both the electron and the nucleus will rotate around the centre of mass of the system, as shown in the following diagram:

The motion around the centre of mass can be taken into account in the Bohr theory by using a standard trick of classical mechanics, in which the rotation of the electron-nucleus system can be replaced by an equivalent system, in which the electron rotates about the position of the nucleus. However, for this equivalence to hold, the electron must be assigned an effective mass, which is referred to as the reduced mass.

Consider the situation in the following diagram.

The top half of the diagram shows the original system in which both the electron (mass m) and the nucleus (mass M) rotate about the centre of mass. From the definition of the center of mass, we must have

The lower half of the diagram shows the equivalent system with which we wish to replace the original rotating system. There are several ways to deduce the required reduced mass of the electron. One is to note that the total angular momenta of the original and equivalent systems must be equal. This leads to the following condition:

From these two equations it is easy to show that the reduced mass is given by

(In figure,

Note that R+X=r, the distance between nucleus and electron in H-atom. Thus, the modified equations for the radii and energies of the electron orbits are:

It can be seen that the correction to the energy levels by assuming rotation about the centre of mass is equal to

Noting that a proton has a mass about 1836 times greater than that of an electron, it can be seen that the magnitude of the correction is C ~ 1836 / 1837 = 0.99946. In other words, the magnitude of the deviation is very small. Note that because the correction C is less than unity, all the energy levels have in fact increased, since they have become less negative.