ATOMIC STRUCTURE

Kotz Ch 7 & Ch 22 (sect 4,5)

properties of light spectroscopy quantum hypothesis hydrogen atom Heisenberg Uncertainty Principle orbitals

ELECTROMAGNETIC RADIATION
subatomic particles (electron, photon, etc) have both PARTICLE and WAVE properties Light is electromagnetic radiation crossed electric and magnetic waves: Properties : Wavelength, l (nm) Frequency, n (s-1, Hz) Amplitude, A constant speed. c 3.00 x 108 m.s-1

Electromagnetic Radiation (2)

wavelength Visible light

Amplitude

wavelength Ultaviolet radiation

Node

Electromagnetic Radiation (3)

All waves have: frequency units: and wavelength

symbol: n (Greek letter nu) cycles per sec = Hertz

l (Greek lambda)
distance (nm)

All radiation:

ln = c

where c = velocity of light = 3.00 x 108 m/sec

Note: Long wavelength small frequency Short wavelength high frequency

increasing frequency

increasing wavelength

Electromagnetic Radiation (4)

Example: Red light has l = 700 nm. Calculate the frequency,

c = n= l

n.

3.00 x 108 m/s

7.00 x 10-7 m

= 4.29 x 1014 Hz

Wave nature of light is shown by classical wave properties such as interference diffraction

Quantization of Energy
Max Planck (1858-1947) Solved the ultraviolet catastrophe

4-HOT_BAR.MOV

Plancks hypothesis: An object can only gain or lose energy by absorbing or emitting radiant energy in QUANTA.

Quantization of Energy (2)

Energy of radiation is proportional to frequency.

E = hn
where h = Plancks constant = 6.6262 x 10-34 Js
Light with large l (small n) has a small E. Light with a short l (large n) has a large E.

Photoelectric Effect
Albert Einstein (1879-1955)

Photoelectric effect demonstrates the particle nature of light. (Kotz, figure 7.6)
No e- observed until light of a certain minimum E is used. Number of e- ejected does NOT depend on frequency, rather it depends on light intensity.

Photoelectric Effect (2)

Classical theory said that E of ejected electron should increase with increase in light intensity not observed! Experimental observations can be explained if light consists of particles called PHOTONS of discrete energy.

Energy of Radiation
PROBLEM: Calculate the energy of 1.00 mol of photons of red light. l = 700 nm n = 4.29 x 1014 sec-1 E = hn = (6.63 x 10-34 Js)(4.29 x 1014 sec-1) = 2.85 x 10-19 J per photon
E per mol = (2.85 x 10-19 J/ph)(6.02 x 1023 ph/mol) = 171.6 kJ/mol
- the range of energies that can break bonds.

Atomic Line Spectra

Bohrs greatest contribution to science was in building a simple model of the atom. It was based on understanding the SHARP LINE SPECTRA of excited atoms.
Niels Bohr (1885-1962)

(Nobel Prize, 1922)

Line Spectra of Excited Atoms

Excited atoms emit light of only certain wavelengths The wavelengths of emitted light depend on the element. H Hg Ne

Atomic Spectra and Bohr Model

One view of atomic structure in early 20th century was that an electron (e-) traveled about the nucleus in an orbit.

Electron orbit

1. Classically any orbit should be possible and so is any energy.

2. But a charged particle moving in an electric field should emit energy. End result should be destruction!

Atomic Spectra and Bohr Model (2) Bohr said classical view is wrong. Need a new theory now called QUANTUM or WAVE MECHANICS. e- can only exist in certain discrete orbits called stationary states. e- is restricted to QUANTIZED energy states.

Energy of state = - C/n2

where

C is a CONSTANT n = QUANTUM NUMBER, n = 1, 2, 3, 4, ....

Atomic Spectra and Bohr Model (3)

Energy of quantized state = - C/n2

Only orbits where n = integral number are permitted.

Radius of allowed orbitals = n2 x (0.0529 nm) Results can be used to explain atomic spectra.

Atomic Spectra and Bohr Model (4) If e-s are in quantized energy states, then DE of states can have only certain values. This explains sharp line spectra.
E = -C (1/22) H atom

n=2
07m07an1.mov

E = -C (1/12)

n=1
4-H_SPECTRA.MOV

Atomic Spectra and Bohr Model (5)

Calculate DE for e- in H falling from n = 2 to n = 1 (higher to lower energy) . DE = Efinal - Einitial = -C[(1/12) - (1/2)2] = -(3/4)C (-ve sign for DE indicates emission (+ve for absorption) since energy (wavelength, frequency) of light can only be +ve it is best to consider such calculations as DE = Eupper - Elower C has been found from experiment. It is now called R, the Rydberg constant. R = 1312 kJ/mol or 3.29 x 1015 Hz Energy n=2

n=1

so, E of emitted light = (3/4)R = 2.47 x 1015 Hz and l = c/n = 121.6 nm (in ULTRAVIOLET region)

This is exactly in agreement with experiment!

Hydrogen atom spectra

High E Short l High n

Low E Long l Low n

Visible lines in H atom spectrum are called the BALMER series.

6 5 4

Energy

3 2

En = -1312 n2

Ultra Violet Lyman

Visible Balmer

Infrared Paschen

From Bohr model to Quantum mechanics

Bohrs theory was a great accomplishment and radically changed our view of matter. But problems existed with Bohr theory
theory only successful for the H atom. introduced quantum idea artificially.

So, we go on to QUANTUM or WAVE MECHANICS

Quantum or Wave Mechanics

Light has both wave & particle properties de Broglie (1924) proposed that all moving objects have wave properties.

For light: E = hn = hc / l
L. de Broglie (1892-1987)

For particles: E = mc2 Therefore, mc = h / l

(Einstein)

and for particles (mass)x(velocity) = h / l

l for particles is called the de Broglie wavelength

WAVE properties of matter

Electron diffraction with electrons of 5-200 keV - Fig. 7.14 - Al metal
Davisson & Germer 1927

Na Atom Laser beams

l = 15 micometers (mm)
Andrews, Mewes, Ketterle M.I.T. Nov 1996
The new atom laser emits pulses of coherent atoms, or atoms that "march in lock-step." Each pulse contains several million coherent atoms and is accelerated downward by gravity. The curved shape of the pulses was caused by gravity and forces between the atoms. (Field of view 2.5 mm X 5.0 mm.)

4-ATOMLSR.MOV

Quantum or Wave Mechanics

Schrodinger applied idea of ebehaving as a wave to the problem of electrons in atoms. Solution to WAVE EQUATION gives set of mathematical expressions called
E. Schrodinger 1887-1961

WAVE FUNCTIONS, Y
Each describes an allowed energy state of an eQuantization introduced naturally.

WAVE FUNCTIONS, Y
Y is a function of distance and two
angles. For 1 electron, Y corresponds to an

ORBITAL the region of space

within which an electron is found. Y does NOT describe the exact location of the electron. Y2 is proportional to the probability of finding an e- at a given point.

Uncertainty Principle
Problem of defining nature of electrons in atoms solved by W. Heisenberg. Cannot simultaneously define the position and momentum (= mv) of an electron. Dx. Dp = h At best we can describe the position and velocity of an electron by a PROBABILITY DISTRIBUTION,

W. Heisenberg 1901-1976

2 which is given by Y

Wavefunctions (3)

Y2 is proportional to the probability

of finding an e- at a given point.
4-S_ORBITAL.MOV (07m13an1.mov)

Orbital Quantum Numbers

An atomic orbital is defined by 3 quantum numbers: n l ml Electrons are arranged in shells and

subshells of ORBITALS . n shell l subshell ml designates an orbital within a subshell

Quantum Numbers

Symbol

Values

Description

n (major)

1, 2, 3, ..

Orbital size and energy = -R(1/n2) Orbital shape or type (subshell)

Orbital orientation in space

l (angular)

0, 1, 2, .. n-1

ml (magnetic)

-l..0..+l

Total # of orbitals in lth subshell = 2 l + 1

Shells and Subshells

For n = 1, l = 0 and ml = 0 There is only one subshell and that subshell has a single orbital (ml has a single value ---> 1 orbital)

This subshell is labeled s (ess) and we call this orbital 1s

Each shell has 1 orbital labeled s. It is SPHERICAL in shape.

s Orbitals
All s orbitals are spherical in shape.

p Orbitals
For n = 2, l = 0 and 1 There are 2 types of orbitals 2 subshells For l = 0 ml = 0 this is a s subshell For l = 1 ml = -1, 0, +1 this is a p subshell with 3 orbitals

Typical p orbital

planar node

When l = 1, there is a PLANAR NODE through the nucleus.

p orbitals (2)
pz

90 o

px py

A p orbital

The three p orbitals lie 90o apart in space

l= n=

px

py

pz
p-orbitals(3)

d Orbitals
For n = 3, what are the values of l?

l = 0, 1, 2
and so there are 3 subshells in the shell. For l = 0, ml = 0 s subshell with single orbital

For l = 1, ml = -1, 0, +1 p subshell with 3 orbitals For l = 2, ml = -2, -1, 0, +1, +2 d subshell with 5 orbitals

d Orbitals
typical d orbital

s orbitals have no planar node (l = 0) and so are spherical.

planar node

p orbitals have l = 1, and planar node have 1 planar node, and so are dumbbell IN GENERAL shaped. the number of NODES d orbitals (with l = 2) = value of angular have 2 planar nodes

quantum number (l)

Boundary surfaces for all orbitals of the n = 1, n = 2 and n = 3 shells

n= 3d

3 2 1
There are

n2
orbitals in the nth SHELL

ATOMIC ELECTRON CONFIGURATIONS AND PERIODICITY

Element Mnemonic Competition

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