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Physical Chemistry: Concepts and Applications

Quantum mechanics (21 lectures) Thermodynamics (17 lectures) Chemical Kinetics (4 lectures)

Quantum Mechanical Principles of Chemical Structure and Bonding


All chemistry depends upon the interactions of electrons in atoms Electrons are quantum mechanical objects. We cannot measure their exact positions and momenta We can, however, obtain the probability distributions of electrons in atoms, molecules, solids and disordered materials, from experiment as well as theory Simple theories of chemical bonding: approximate idea of electron distributions Quantum chemistry: how to calculate the electron distributions and electronic properties of materials

How do we visualize bonds?

Microscope

X-ray diffraction

1-thiocoumarin

Lewis lone pairs on Oxygen Extra electron density on sulfur atom -bonds: electron density concentrated along bond axis
P.Munshi and T.N.Guru Row, Acta Crystallographica A , 2002,58,354

How do we get to know H2O?


O
How do we calculate bond energies? How do we find the shapes of molecules? How do we check if VSEPR theory is right?

H H Covalent bonds

H
Dipole moment: 1.8 D O Bond angle: 104.45 Deg Bond length: 0.9584 Ang

H Lone pairs can form hydrogen bonds

Organization
Principles of Quantum Mechanics Simple, exactly solvable problems Hydrogen Atom Many-electron Atoms Molecules

Books
Atkins, Physical Chemistry Alberty and Silbey, Physical Chemistry

Quiz before Minor I

Wave-Particle Duality
In classical physics, there is a clear distinction between waves and particles The development of quantum mechanics became necessary in order to explain experiments which suggested that electromagnetic waves could behave like particles Classical Particles Classical Waves Evidence for particle nature of electromagnetic waves Wave-Particle Duality: The de Broglie Hypothesis Experiments to verify the wave nature of particles

Classical Particles
Obey Newtons laws of motion

d 2x m 2 =F dt

Characteristic mass: inertial/gravitational mass In principle, the position and velocity can be specified simultaneously to arbitrary accuracy Completely predictive or deterministic: If the initial position, momentum are known and the forces acting on a particle can be calculated, then the entire trajectory (r(t),v(t)) can be predicted exactly using Newtons laws Very successful on a macroscopic scale: planetary orbits, geostationary satellites, rocket launches Sometimes works on a molecular scale: kinetic theory of gases

Classical Waves
Associated with periodic variations in time and/or space of some property. Identify time period (frequencies, ) or spatial period (wavelengths, ) sound: density water: surface height (ripples) or density light: electric and magnetic fields Require periodic functions to describe waves which must be solutions of special types second-order differential equations 1-dimensional stationary wave equation d2 = k 2 d 2 x 3-Dimensional time-dependent wave equation d 2 d 2 d 2 1 d 2 + + = 2 2 2 2 dx dy dz c dt 2 Interference/Diffraction: Combining periodic functions generates other periodic functions Periodicity will be observable if we make measurements on length scales less than and time scales less than

Experimental Evidence for Particle Nature of Radiation


Black-body radiation Photoelectric effect Compton Effect Absorption/Emission of Radiation by Atoms

The Photoelectric Effect (1905)


Light exists in the form of distinct packets or quanta of energy, h An electron can be ejected from a metal surface only if a single quantum of incident light has energy greater than the workfunction of the metal () Kinetic energy of emitted electron =

1 mv 2 = h 2

Compton Effect (1923)


The observed shift in X-ray wavelength Is given by:

Compton could explain this by: (i) Conservation of energy where K.E. of electron was calculated relativistically (ii) Conservation of momentum assuming that the X-ray photon had momentum, p=h/

Wave-Particle Duality: The De Broglie Equation (1924)


Expts showed that a photon could have well defined energy as well as momentum De Broglie considered the properties of radiation quanta, using the result from relativity theory that a particle of zero rest mass moving at velocity c will have momentum p=E/c=h/

h c h h = = = = h v E/c p

By analogy, a non-relativistic particle of mass m and velocity v will have a wavelength


Plancks constant Wave property

. h =

p
Particle property

Matter Waves
Plancks constant determines the length scale on which the wave properties of particles with non-zero mass become important How can one generate de Broglie waves of different wavelengths Charged particles can be accelerated through a fixed electrical potential energy difference Thermal kinetic energy of uncharged particles will also result in a welldefined wavelength Particle Electron Kinetic energy 1eV 100eV 10000eV Proton 1 KeV 1 MeV 1 GeV Neutron 1.5RT/NA (Thermal K.E.) (Angstrom) 12.2 1.2 0.12 0.009 28.6 Fermi 0.73 Fermi 1.5

h = 6.63 10 34 Js

Measuring matter waves: Bragg scattering

n = 2d sin

Electron Diffraction: Davisson-Germer Experiment (1927)

Double-Slit Experiment with a Single Electron (2006)

Hitachi devised a detector that could detect a single electron at a time with almost 100% efficiency. The detector would register a signal only when electron waves would pass on both sides of the electron biprism at once.

www.illuminatingscience.org/2006/10/

Diffraction of small helium clusters

Question: Each line is marked by the cluster size N. Can you explain the spacing between lines?

http://www.gwdg.de/~mpisfto/atom_optics_e.html

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