Quantum Mechanics and Atomic Theory

An in-depth view of the atom and its components (mainly electrons)

Atomic Structure (a brief introduction)

An atom consists of a small nucleus (D ~ 10-13 cm) surrounded by electrons moving at an average distance 10-8 cm away) The nucleus contains protons and neutrons and is very small and very dense The proton and neutron masses are roughly the same while electrons are much smaller The number and arrangement of the electrons determine the properties of the atoms
Particle Neutron Proton Electron Mass 1.67 x 10 -27 kg 1.67 x 10 -27 kg 9.11 x 10 -31 kg Charge 0 +1 -1

Isotopes

Quantum Mechanics
Around two hundred years ago, scientists proposed the existence of the atomic model (matter is made up of basic units). Basic stoichiometric experiments cemented this belief. The next logical question was what are atoms and what are they made up of. Periodic trends can be explained by knowing about the atoms and the electrons in the context of quantum mechanics Quantum mechanics was a brand new area of physics that was able to explain many of the observations regarding electrons in the early 1900s

Electromagnetic (EM) Radiation

Energy travels through space via electromagnetic radiation (not exclusively)
Sun light Microwave energy X-rays Radiowaves, etc.

All these types of energy experience wavelike behaviour and as such are characterized by:
Wavelength Frequency Speed

The name electromagnetic is derived from the fact that it has an electric field and a magnetic field that travel perpendicular to each other

Describing EM radiation

The electromagnetic spectrum

Which have higher frequency: Gamma rays or radiowaves? Which has higher frequency: blue light or red light? What is your perception about the energy of different radiation?

Example
The wavelength (colour) that humans can see best is 555 nm (yellowish green) Calculate the frequency this light c = , = c/
(3.00*108 m/s) / (555 nm * 10-9 m/nm) = 5.41*1014 s-1 = 5.41*1014 Hz

Calculate the wavelength corresponding to 480 THz? What colour does that correspond to? 480 THz = 480*1012 Hz = 4.80*1014 s-1 = c/

(3.00*108 m/s) / (4.80*1014 s-1) = 6.25*10-7 m = 625 nm Red

The Blackbody Experiment

About 120 years ago it was common knowledge that matter and energy were distinct Matter was made up of particles (molecules atoms) that can be counted. Energy on the other hand was described by waves. Matter had a mass while energy was continuous and delocalized. Experiments in the early 1900s started to prove otherwise One of the first experiments was considered by Max Planck. He studied the profile intensity of EM radiation as a body is heated to incandescence.

The Blackbody Experiment

A hot object radiates energy over a broad range of wavelengths (frequencies). The energy radiated at a given frequency increases as the frequency increases, reaches a maximum, then declines as frequency increases further. The maximum energy frequency increases as the temperature increases, thus the color of an incandescent object depends on its temperature. Cooler objects are more red, while hotter objects are white or even blue. Classical physics had difficulty explaining the reason for the declining emission at shorter wavelengths. Planck suggested that EM waves cannot possess just any frequency but only specific frequencies. In more detail, he discovered that energy could only be a whole number multiple of h http://www.youtube.com/watch?v=l_t8dn4c6_g

Quantized Energy

Photoelectric Effect

Practice problems - Energy and Wavelength

What is more energetic X-rays (10-10 m) or microwaves (10-2)? It takes 208.4 kJ of energy to remove one mole of electrons from the atoms on the surface of rubidium metal. If Rb-metal is irradiated with 254 nm light, what is the maximum KE the released electrons can have? (208.4 kJ/mole) / (6.022*1023 e-/mole) = 3.4606*10-22 kJ/e- = 3.4606*10-19 J/e E = h = hc/ = (6.626*10-34 Js * 2.998*108 m/s)/254*10-9 m = 7.8207*10-19 J 7.82*10-19 J - 3.46*10-19 J = 4.36*10-19 J

Energy and Mass

Summary
Energy is quantized It can only be transferred in small packets called quanta EM radiation appears to have some particle like properties. This effect is known as the dual nature of light. Does matter also have dual nature?

Does matter exhibit wavelike properties?

EM radiation exhibits particle-like properties. Matter exhibits both particulate and wave properties. Big pieces of matter exhibit only particle like properties Small pieces of matter exhibit mostly wavelike properties Pieces of matter with an intermediate size have both properties

Atomic Spectrum of Hydrogen

When a high-energy discharge is passed through a sample of hydrogen gas, the H2 molecules absorb energy which causes the HH bonds to break. The resulting atoms absorb energy (are excited), the energy is then released by emitting light of different wavelengths. The white light emitted by an incandescent object has a broad spectrum that covers all energies, but the light emitted by the hydrogen atoms has a purplish hue and only few lines with well defined wavelengths are observed. The hydrogen emission spectrum is called a line spectrum. This suggests that there are only a select group of energies for an electron in a hydrogen atom. In other words the electron in the hydrogen atom is quantized.

 (nm)

The Bohr Model

Niels Bohr developed a quantum model for the H atom which was loosely based upon the orbits the planets in our solar system

Each energy level was found to correspond to a specific orbit for the electron about the nucleus. Each orbit, or principal quantum number n, where n = 1 is the lowest energy level (ground state), n = 2,3,4,5,etc. are excited states and n = is the point at which the electron and the nucleus no longer interact (i.e. the electron has been promoted completely out of the atom).

Bohr Model

Bohr model

Compare the energy when the electron is closest to the nucleus to when the electron is ionized The lowest energy of the electron is called the ground state Calculate the energy when the electron is in level 4 Calculate the energy when the electron is in level 1 Calculate the change in energy as the electron moves from level 4 to level 1. Does the sign make sense What wavelength corresponds to this energy?

Electronic Transitions

Example
An excited hydrogen atom emits light with a wavelength of 397.2 nm to reach the energy level for which n = 2. In which principal quantum number did the electron begin? E = h = hc/ = (6.626*10-34 Js * 2.998*108 m/s) / 397.2*10-9 m = 5.0012*10-19 J E = -2.178*10-18 J * (1/n2 1/22) 5.0012*10-19 J / -2.178*10-18 J = -0.22962 = (1/n2 1/4) -0.22962 + 0.25 = 0.020376 = 1/49 = 1/72 n=7

Example
Consider an electron for a hydrogen atom in an excited state. The maximum wavelength of electromagnetic radiation that can completely remove (ionize) the electron from the H atom is 1460 nm. Determine the initial excited state for the electron? E = h = hc/ = (6.626*10-34 Js * 2.998*108 m/s) / 1460*10-9 m = 1.360599*10-19 J E = -2.178*10-18 J * (0 1/n2) 1.360599*10-19 J / -2.178*10-18 J = -0.062470 = (-1/n2) 0.062470 = 1/16 = 1/42 n=4

What about other atoms than hydrogen?

The Quantum Mechanical Description of the Atom

Heisenberg, de Broglie and Schrdinger contributed to develop a new atomic model that works for all atoms (unlike the Bohr model). The approach developed by de Broglie and Schrdinger became known as wave mechanics or quantum mechanics. de Broglie showed that electrons can behave like waves (remember diffraction patterns?) To Schrdinger and de Broglie the electron bound to the nucleus seemed like a standing wave.

Standing Waves
Standing waves are found in guitars, violins, etc. A string attached at both ends The dots are called the nodes. They are the points of zero movement of the waves de Broglie and Schrdinger demonstrated that there are only some circular orbits with a circumference that into which a whole wavelength will fit Other orbits produce destructive interference and do not exist This observation provides an explanation for the quantization of energies in the hydrogen atom

The Schrdinger Equation

The Heisenberg Uncertainty Principle

Example
Calculate the minimum uncertainty in position for: an electron with v = 0.100 m/s how does this number relate to the size of an atom? a chemistry instructor (m = 65 kg, v = 10 km/h, uncertainty in velocity is 0.1 km/h) how does this number relate to the size of an instructor?