Peter Atkins Julio de Paula !

Atkins Physical Chemistry

Eighth Edition

Chapter 8 Quantum Theory: Introduction and Principles !

Copyright 2006 by Peter Atkins and Julio de Paula

Topics!
! Blackbody radiation ! ! Limitation of classical mechanics for atomic systems! ! Wave-particle duality! ! Photoelectric effect! ! Schrdinger equation! ! Free particle wavefunction! ! Operators! ! Uncertainty principle!

Blackbody radiation!

Figure 1.1!

Energy distribution! of blackbody radiation!

Blackbody radiation! ! Prediction of classical! mechanics agrees with ! observation at low ! frequencies (high wavelengths) but fails ! at high frequencies (small wavelengths)! !

Plancks distribution!

Heat capacities of solids!

Classical mechanics cannot accurately predict the temperature dependence of heat capacities of solids

Atomic and molecular spectra are composed of discrete lines!

Photoelectric effect! Classical theory ! ! Electrons are emitted at all

frequencies, provided the light intensity is high! ! Kinetic energy of the electrons increases with intensity of light!

Experiment! ! # of emitted electrons depend on the

light intensity but not their kinetic energy! ! No electrons emitted unless the frequency of the light exceeds a threshold value! ! Kinetic energy of the ejected electrons depend on the frequency of the incident light! ! Electrons are emitted even at low intensities if the frequency exceeds a threshold value!

http://hyperphysics.phy-astr.gsu.edu/hbase/imgmod2/pelec.gif!

Davisson-Germer Experiment: established wave nature of electrons!

! The experiment (1927) involved scattering of electrons from a single crystal of Ni! ! Diffraction patters exhibited wave behavior! ! Landmark experiment that showed wave nature of matter! ! Conrmed the prediction of de Broglie three years ago!

Wave-particle duality!

Source: google images!

Behavior of matter at temperatures close to absolute zero! Formation of Bose-Einstein condensates!

400 nK

200 nK

50 nK

http://cua.mit.edu/ketterle_group/Animation_folder/BEC_phase_transition.htm!

Wavefunctions describing systems with high kinetic energies (high momenta) are highly oscillatory!

Real and imaginary part of a plane wave describing motion of a free particle!

Square of the wave function denotes probability of nding the particle in a given region!

Volume element for integration of the wave function in three dimensions, d"=dxdydz!

Wave function is an amplitude function: it may have positive an negative amplitudes but the square of the wave function, |#|2 (probability) is always a positive quantity.!

Volume element in spherical polar coordinates d"=dxdydz=r2drsin$d$d%!

Acceptable wave function must be nite, single-valued and continuous!

Quantum mechanical postulates!

! The state of a quantum mechanical system completely specied by its wave function #. The square of the wave function, #(x)*#(x) give the probability of nding the particle at a location x.! ! For every measurable property, there exists a corresponding operator. An experiment in the lab to measure the value of the property is equivalent to operating the corresponding operator on the wave function of the system.! ! In any single measurement of the observable corresponding to an operator, the only value that ever will be measured is the eigen value of the operator! ! The average value of an observable is the expectation value of #d& its operator: ! " = # *%