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Chem.

266 Physical Chemistry III


Quantum Mechanics

Instructor: Assoc. Prof. Joel R. Salazar

Office: Dept. of Chemistry, CAS, CLSU E-mail: chemistjoel2004 @yahoo.com Consultation Hours: Monday

The Course
Prerequisite Chemistry 250/260
Resources Physical Chemistry By : P.W.Atkins, Alberty, Levine, Ball, Laidler, Castillan Physical Chemistry : A Molecular Approach By. D. Mc Quarrie Lectures (principles, procedures, interpretation, tricks, insight) Homework problems and solutions

Course Planner

o o o o

Material covered in lectures. What to focus on or review. What to study from the book. Homework assignments. Questions for further thinking.

Grading Policy
Homework 10% (Generally, chapter assignment)

Quiz
Exams

40 %
50 %

Please turn in homework on time!

Development of Quantum Mechanics


Chem. 260 Lecture Notes

Quantum Mechanics and Quantum Chemistry


Quantum Chemistry Application of quantum mechanics to problems in chemistry Quantum Mechanics Laws governing the behavior of very small particles Determines the properties of nanomaterials (1 to 100 nm)

Electronic Structure of Atom


From studies of the properties of light or radiant energy also called electromagnetic radiation.

Nature of the Electromagnetic Radiation


All radiant energy has wavelike characteristics ( analogous to those of waves that move through water) Properties of any kind of wave i.) wavelength () ii.) frequency () iii.) velocity iv.) amplitude

Properties of any kind of wave


1.) wavelength = the distance between two neighboring crests or through of a wave = measured in terms of nm 2.) frequency = number of waves/second = represented as cycles /second or Hertz (Hz) 3.) velocity = distance traveled by the wave in one second c=x 4.) amplitude = height of a crest or depth of the trough

Important Notes: Determination of the or frequency of radiation is done by means of a devise known as spectrometer. All electromagnetic radiation travel with the same velocity and may differ in their wavelength and frequency. The velocity of an electromagnetic wave (light) is found to be constant and independent of the medium in which the wave travels ( electromagnetic waves do not require any medium of propagation)

Origins of Quantum Theory


Radiation acts as discrete packets of energy called quanta. 1885- 1908: Atomic spectra (Line spectrum of H gas is an emission spectrum) Hot atoms in an electric discharge emit light. Line spectrum ( set of lines which are well separated)

Atomic Spectra
these are line spectra shown by atoms of elements the spectra of elements are dependent upon the nature of the radiations emitted. Important Notes: 1.) Each line in the spectrum is having a characteristic frequency therefore it will have a definite energy. e.g. Hydrogen Spectrum = consists of a number of discrete lines in the visible and ultraviolet region 2.) The change in the transition state corresponds to the amount of energy absorbed

Atomic Spectra
H atom absorbs only specific 1885 J.J. Balmer (visible light) 1886 Rydberg (u.v light) 1908 Ritz ( Infrared) Balmer showed that for the visible lines of hydrogen, a plot of v (frequency) vs 1/n2 gave a straight line. Rydberg = who put forward that the wavenumber (cm-) of any line of the hydrogen spectrum can be represented as a difference of two terms, one of which is constant and the other varies throughout the series.

Spectral Series and Rydberg integers for the Rydbergs Equation


Series Lyman Balmer Paschen Brackett Pfund n1 1 2 3 4 5 n2 2,3,4 3,4,5 4,5,6 5,6,7 6,7,8 Spectral Region ultraviolet Visible Infrared Infrared Infrared

Sample Problem
Calculate the wavelength of the second line in the Paschen series, and show that this line lies int the near infrared, that is, in the infrared region near the visible Ans: = 1.282 x 10-4 cm =1282 nm

1859 -1901 Black Body Radiation


Radiation given off by materials when they are heated ( one that absorbs and emit all frequencies and serves as an idealization for any radiating material.) E.g. when an object is heated hot enough, it begins to give off light. At first it glows a dull red. As it gets hotter, the red color gets brighter. At high enough temperature it will eventually glow blue. We see that there is a continual shift of the color of a heated sample as temperature increases ( the radiation goes from a lower frequency to a higher frequency.)

Used regularly in astronomy to estimate the surface temperature of stars.


e.g. solar spectrum can be approximated as black body at around 6000K ( this temperature will give the greatest intensity of radiation) If we estimate max to be 500 nm T = 2.90 x 10-3m.K / 500 x 10-9m = 5800 K

1859: Kirchoff
Same behavior of radiation emitted/absorbed for different materials this implies something fundamental about radiation 1879: Stefan Boltzmann Law = aT4 the total energy density is proportional to the fourth power of the temperature. (based from the area of the graph the area increases with the fourth power of the temperature).

Justification: The electromagnetic field inside the container has a definite total energy , which increases as the temperature.
The total energy density is the total energy divided by the volume of the interior of the container.

Alternative form of the Law


Excitance (M) = the power emitted per unit area ( brightness of the emission) M = T4 where = 5.67 x 10-8w/m2K = Stefan Boltzmann constant 1894 : Wein Displacement Law Tmax = 1/5 C2 where C2 = 1.44 cm K (second radiation constant)

1900: Rayleigh Jeans Law


Studied black body radiation from classical viewpoint (v) dv = (8kBT/c3) v2dv where : V dV = radiant energy density between the frequencies v and v + dv ( J/m3)

Limitations
Rayleigh Jeans formula is quite successful at long and low v, but it fails badly at high v and short . This failure is called UV breakdown/ catastrophe (leads to infinite energy). The frequency increases as the radiation enters the ultraviolet region, the divergence in the radiant energy density as v2 (frequency) was termed the ultraviolet catastrophe.

1901: Max Planck (Quantum Theory of Radiation)


The first person to successfully explain black body radiation from the viewpoint of statistical thermodynamics. Classical physics assumed that the light emitted from the black body was caused by oscillations of the electrons (e-) in the object just like oscillations of electrons in an antenna emit radiowaves. Planck hypothesized that the energies of the oscillators were discrete and had to be proportional to an integer multiple of the frequency. E = nhv where: n = 1,2,3 h = Plancks constant

Planck Distribution d= d Where: ( ,t) = (8hc/5) (d/ ehc/kT - 1) ( v,t) = (8hv3 /c3) (dv / ehv/kT - 1)

Important Notes: 1.) Planck formula reduces to the Rayleigh Jeans Law for long radiation.
2.) Planck distribution also accounts for the Stefan Boltzmann and Wien Law

Stefan Boltzmann Law


By integrating the total energy density over all wavelengths from =0 to =

Weins Law
By looking at d/ d = 0

or d(,t) / d = 0 (the condition for the maximum in the distribution ) at low T.

Sample Problem
1.)Equation ( v,t) = (8hv3 /c3) (dv / ehv/kT - 1) expresses Plancks radiation law in terms of frequency. Express Plancks radiation law in terms of . 2.) a.) Derive the Stefan Boltzmann and Wein equations using Plancks distribution of blackbody radiation. b.) Account that Plancks formula reduces to the Rayleigh Jeans law for long wavelength of radiation.

1907: Einstein
Heat Capacity of Solids According to Classical Mechanics The mean vibrational energy of each atom of a solid is 3 KT For solid composed of N atoms, the total vibrational energy : Ev = 3NkT The contribution of the vibrational energy to the molar internal energy UM = 3NkT = 3 RT The molar heat capacity at constant volume is

Cvm = (Um/ T)V = 3R (Law of Dulong and Petit Limitations of Dulong and Petits law
deviations were observed when applied to measure heat capacities at low temp.

Einstein Formula
accounts for the decrease of heat capacity at low temperature. Assumption: Each atom oscillates about its equilibrium position with a single frequency (v).

The molar vibrational energy of the metal Um = (3Nhv)/ (ehv/kT 1)

Bohrs Model of Atom


Postulates of Bohrs about the moving electrons. 1.) Electrons are moving in certain definite paths called orbits which have specific energies. The angular momentum of the electron is an integral multiple of h/2 mvr = nh / 2 where n is any integer 2.) Each stationary state corresponds to a definite quantity of energy associated with it. These may be called energy levels. These energy levels are characterized by an integer n.

Bohrs Model of Atom


3.) The energy level nearer the nucleus has lower energy while that farthest from it has the maximum energy. Electron in the level with lowest energy is said to be in the ground state (most stable state of the atom) 4.) If energy is made available to the electron, it will absorb energies in packets or quanta, so that it could move to a higher energy level.

Bohrs Quantum Theory of H - atom


Bohr obtained an expression for the energy of an electron in H atom as follows: Let: r = radius of the orbit in which an electron is revolving

Assumptions
1.) Force of attraction between the electron and the nucleus 2.) Centrifugal force experienced by the electron ( under the influence of which the electron tends to fly away from the nucleus) 3.) The electron does not fall into the nucleus 4.) Incorporating Bohrs quantum condition 5.) When the electron is excited from n1 to n2 having E1 and E2.

Sample Problem
Find the radius of the Bohr orbit for the most stable state (minimum energy) of a hydrogenic atom. Ans: An electron moving about a nucleus of charge ze in a circular orbit has an angular momentum.

Structure of Atom (Modern Picture)


Defects of the Bohr model of atom It could not explain the atomic spectra of elements other than hydrogen Limitations : 1.) It could not account for the brightness of spectral lines (e.g. the noble gases ) 2.) no justification was given for the basis of quantization of momentum of the electron.

e.g. why the momentum of the electron should have only those values which are integral multiple of h/2 and why not h/3.
3.) could not explain the reason why atoms should combine to form chemical bonds.

Relation Between Momentum and wavelength


Light
Classical model : as wave New model: made up of quanta/pockets (bunch of photon)

Wave Particle duality can be explained through


1.) Photoelectric effect The electromagnetic radiation displays the characteristic of particles (classical physics wave like) 2.) Experiments on Electron diffraction The electrons (classical physics particles) also display the characteristics of waves

Particle Character of Electromagnetic Radiation


Observations 1.) The discrete spectra for atoms and molecules can be pictured as the atom or molecules generating a photon of energy hv where it discards an energy of magnitude E 2.) The energies of electrons produced by the photoelectric effect 3.) The Compton effect

Photoelectric Effect
1905 : Einstein This effect is due to the ejection of electrons from metals when they are exposed to UV light. Essential Features of the Photoelectric effect i.) No electrons are ejected, regardless of the intensity of the radiation, unless its frequency exceeds a threshold value, which is a characteristic of a metal ii.) The kinetic energy of the ejected electrons varies linearly with the frequency of the incident radiation iii.) Even at low light intensities, electrons are ejected immediately if the frequency is above threshold.

Conservation of energy for Photoelectric Effect


K.E. = mv2 = hv where = work function (characteristic of a metal) = energy required to remove an electron if hv < = photoejection cannot occur because the photon brings insufficient energy. The min. frequency that will eject an electron is just the frequency required to overcome the work function of the metal. = hvo where vo = threshold frequency

Sample Problem
When Lithium is irradiated with light, the kinetic energy of the ejected electron is 2.935 x 10-19J for = 300.0 nm. Calculate the threshold frequency and the work function of lithium from these data. Ans. Vo = 5.564 x 1014 Hz = 3.687 x10 -19 J = 2.301 eV

Compton Effect
The photons were observed to be scattered at all angles by the electrons of the scattering material.

Arthur Compton = investigated the scattering of monochromatic x -rays by a target such as a piece of graphite. The scattered beam consisted of a radiation of 2 different wavelength's.

The Wave Character of electron


1.) Davisson and Germers Observed the diffraction of electrons by a crystal 2.) G.P Thomson Showed that a beam of electron was diffracted when passed through a thin gold foil 3.) Louis de Broglie Suggested that any particles, not only photon travelling with a momentum (p) should have a .

Quantization of Momentum
Assumptions: i.) the electron wave is moving in a circle ii.) the motion of the electron should be in phase ( so that the electron will continuously move in a circular orbit) Circumference of circular orbit = integral multiple of its wavelength 2r = n where : r = radius of the orbit = wavelength of electron wave

Quantization of Momentum
From de Broglie relationship = 2r / n Comparing the two equations mvr = nh / 2 Bohr Postulate mvr = angular momentum of the electron Standing wave = the distance between two points will not change with time Only integral numbers of s will form a standing waves

Dual Nature of Matter

Louis de Broglie
1924: Louis de Broglie Concluded that energy is associated with both light and matter (particle) Electrons have both particle and wave properties ( every particle can be considered to have an associated and wave properties) = h/mc = h/mv de Broglie equation

2 r = n wave like properties P = mv particulate properties P = h/ complementary properties


Sample Problem What is the of a 2000 kg vehicle moving at 100 km/h?

Implications of de Broglie Equation


In order to obtain a full mechanical description of a free particle (no forces acting on it) there must be a wavelength and hence some simple oscillating function associated with the particles description. This function can be a sine, cosine, or equivalently, a complex exponential function

Sample Problem
Estimate the wavelength of electrons that have been accelerated from rest through a potential difference of 1.00 kV Hint: EK = mev2 = p2/2me Where: p = mev The energy acquired by electron that falls through a potential difference is given by: e x p = 2mee and = h / p Ans. 3.88 x 10-11m

Periodic Property of a Wave


In 1926 Schrdinger formulated his famous equation by applying the de Broglie relationship to the classical wave equation (written below in one dimension):

Heisenberg and Schrdinger ( Quantum Mechanics)


Schrdinger ( partial differential equation) and Heisenberg (matrices) to describe wave behavior

Fundamental principle of Nature : Heisenberg Uncertainty principle


States that it is not possible to specify both the position and the momentum of a particle simultaneously with infinite precision.

p . x /2 or h/4
Likewise for simultaneous measurements of E and time

E . t /2

Sample Problem
Calculate the uncertainty in the position of a baseball(5.0 oz) thrown at 90mph if we measure its momentum to a millionth of 1.0 %. Ans. p = 5.6 kgm/s; 1mile = 1610 m; 1lb = 16oz x = 1.2 x 10-26 m

Quantum Mechanics
The basic concept is energy is quantized e.g. spectrum of a solution Basically statistical in nature ( probabilistic approach) = knowing the state, we cannot predict the result of a position measurement with certainty, we can only predict the probabilities of various possible results Associated with each physical observable ( position, momentum and energy) is a mathematical operator. From these operator we can predict the behavior of a physical system

Quantum Mechanics provide:


1.) the possibility of calculating energy levels and other properties of atoms and molecules 2.) the explanation of the periodic table 3.) the basis for understanding spectroscopy 4.) the understanding of the nature of the chemical bond

Application of Quantum Mechanics


1.) Calculations show why properties such as IP, EA and atom size vary in complicated way 2.) Energy levels, bond lengths and bond angles may be calculated quite accurately for many small molecules 3.) Spectroscopy is useful in identifying molecules identity and determining their concentration

Application of Quantum Mechanics


A.) Microwave and Far IR Provide information on internuclear distances and bond angles B.) IR and Raman Spectroscopy Provide information about vibrational frequencies C.) Visible and Ultraviolet Provide information on dissociation energies and electronic excited states

Failure of Classical Mechanics


Classical mechanics cannot be applied at microscopic levels because it is incapable of treating such factors as i.) electromagnetic radiation acting as photons, ii.)photons having momentum, iii.)matter particles showing dual behavior.

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