Chapter 6 Electronic structure of atoms

light photons spectra Heisenbergs uncertainty principle atomic orbitals electron configurations the periodic table

Chapter 6 Electronic structure of atoms

6.1 The wave nature of light
Visible light is a form of electromagnetic radiation

Radiation carries energy through space

Electromagnetic radiation can be imagined as a self-propagating transverse oscillating wave of electric and magnetic fields.

The number of waves passing a given point per unit of time is the frequency

For waves traveling at the same velocity, the longer the wavelength, the smaller the frequency. All electromagnetic radiation travels at the same velocity

The wavelength and frequency of light is therefore related in a straightforward way:

Q. What is the wavelength of UV light with v = 5 x 1015 s-1?

Q. What is the frequency of electromagnetic radiation with a wavelength of 0.5 m?

Wave nature of light successfully explains a range of different phenomena.

Thomas Youngs sketch of two-slit diffraction of light (1803)

6.2 Quantized Energy and Photons

1. Blackbody radiation

2. The photoelectric effect

3. Emission spectra

Hot Objects and the Quantization of Energy

Heated solids emit radiation (blackbody radiation)

In 1900, Max Planck investigated black body radiation, and he proposed that energy can only be absorbed or released from atoms in certain amounts

The relationship between energy, E, and frequency is:

The Photoelectric Effect and Photons The photoelectric effect provides evidence for the particle nature of light and for quantization.

Einstein proposed that light could have particle-like properties, which he called photons.

Light shining on the surface of a metal can cause electrons to be ejected from the metal.

Below a threshold frequency no electrons are ejected

Light has wave-like AND particle-like properties

Q. MRI body scanners operate with 400 MHz radiofrequency energy. How much energy does this correspond to in kilojoules/mol?

Q. A mole of yellow photons of wavelength 527 nm has __________ kJ of energy.

6.3 Line Spectra and the Bohr Model

Line spectra
Radiation composed of only one wavelength is called monochromatic.

When radiation from a light source, such as a light bulb, is separated into its different wavelength components, a spectrum is produced,

White light passed through a prism provides a continuous spectrum

Bohrs Model Rutherford assumed that electrons orbited the nucleus analogous to planets orbiting the sun; however, a charged particle moving in a circular path should lose energy

Niels Bohr noted the line spectra of certain elements and assumed that electrons were confined to specific energy states.

1. Only orbits of specific radii are permitted for electrons in an atom 2. An electron in a permitted orbit has a specific energy 3. Energy is only emitted or absorbed by an electron as it moves from one allowed energy state to another

The Energy States of the Hydrogen Atom Colours from excited gases arise because electrons move between energy states in the atom.

Bohr showed mathematically that

where n is the principal quantum number (i.e., n = 1, 2, 3) and RH is the Rydberg constant.

The first orbit in the Bohr model has n = 1 and is closest to the nucleus.

Electrons in the Bohr model can only move between orbits by absorbing and emitting energy (E = hn). The ground state = the lowest energy state

The amount of energy absorbed or emitted by moving between states is given by

Q. When the electron in a hydrogen atom moves from n = 6 to n = 2, is light emitted or absorbed? Q. What is its wavelength in nm?

Limitations of the Bohr Model The Bohr Model has several limitations:

However, the model introduces two important ideas: 1. the energy of an electron is quantized: electrons exist only in certain energy levels described by quantum numbers

6.4 The wave behavior of matter

Louis de Broglie posited that if light can have material properties, matter should exhibit wave properties

de Broglie proposed that the characteristic wavelength of the electron or of any other particle depends on its mass, m, and on its velocity, v

Matter waves is the term used to describe wave characteristics of material particles.

Q. What is the wavelength of a bullet (7.5 g) traveling at 700 ms-1? Q. At what speed must a 3 mg object be moving in order to have a de Broglie wavelength of 5.4 10-29 m?

The Uncertainty Principle

sets a fundamental limit on how precisely we can know the location and momentum of an object.

Heisenberg imagined a gamma ray microscope to explain his uncertainty principle.

Heisenberg related the uncertainty of the position, x, and the uncertainty in momentum (mv) to a quantity involving Plancks constant:

1) Consider that I am walking at 100 ms-1, and you can measure my velocity within 1%. What is the minimum uncertainty in my position?

2) Consider now that I am an electron walking at 100 ms-1, and you can still measure my velocity within 1%. What is the minimum uncertainty in my position?

6.5 Quantum Mechanics and Atomic Orbitals

Erwin Schrdinger proposed an equation containing both wave and particle terms. The solution of the equation is known as a wave function, (psi).

Orbitals and quantum numbers If we solve the Schrdinger equation we get wave functions and corresponding energies.

The probability density (or electron density) described by an orbital has a characteristic energy and shape. The energy and shape of orbitals are described by three quantum numbers. These arise from the mathematics of solving the Schrdinger equation.

must be a positive integer n = 1,2,3,4,

maximum value is (n-1), i.e. = 0,1,2,3(n-1) use letters for (s, p, d and f for = 0, 1, 2, and 3). maximum value depends on , can take integral values from to + Q. Tabulate the relationship among values of n, and m through n = 4.

Orbitals can be ranked in terms of energy.

6.6 Representations of Orbitals

The s orbitals All s orbitals are spherical As n increases, the s orbitals get larger As n increases, the number of nodes increases

The p orbitals p orbitals are dumbell-shaped 3 values of m

The d orbitals
d orbitals have two nodes at the nucleus

6.7 Many-Electron Atoms

Orbitals and Their Energies In a many-electron atom, for a given value of n, the energy of an orbital increases with increasing value of

Therefore, the energy-level diagram looks slightly different for many-electron systems Electron Spin and the Pauli Exclusion Principle Line spectra of many-electron atoms show each line as a closely spaced pair of lines.

Stern and Gerlach designed an experiment to determine why. A beam of atoms was passed through a slit and into a magnetic field and the atoms were detected:

Two spots were found, corresponding to silver atoms with electron spinning one way or the other

Stern and Gerlach designed an experiment to determine why. A beam of atoms was passed through a slit and into a magnetic field and the atoms were detected:

How do we show spin? Paulis exclusion principle states that:

6.8 Electron Configurations

Electron configurations tell us how the electrons are distributed among the various orbitals of an atom.

When writing ground-state electronic configurations:

Li

Hunds Rule For degenerate orbitals, the lowest energy is attained when the number of electrons with the same spin is maximized

Q. Draw the electron configurations of Li, Be, B, C, N, O, Ne and Na.

Condensed Electron Configurations Electron configurations may be written using a shorthand notation (condensed electron configuration): 1. Write the core electrons corresponding to the noble gas in square brackets

2. Write the valence electrons explicitly

Q. Draw the condensed electron configurations of Li, Na and P.

Transition Metals

The block of the periodic table in which the d orbitals are filling represents the transition metals.

6.9 Electron Configurations and the Periodic Table

The periodic table can be used as a guide for electron configurations.

Blocks of elements in periodic table relate to which orbital is being filled

Anomalous Electron Configurations

There are elements that appear to violate the electron configuration guidelines:

When atomic number > 40, energy differences are small and other anomalies often occur. These usually act to reduce electron repulsions.