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Part II Lesson 1 It's a quantum world: The theory of quantum ...
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1.021, 3.021, 10.333, 22.00 : Introduction to Modeling and Simulation : Spring 2012
Part II – Quantum Mechanical Methods : Lecture 1
It’s A Quantum World: The Theory of Quantum
Mechanics Jeffrey C. Grossman
Department of Materials Science and Engineering Massachusetts Institute of Technology
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3.021 Content Overview I. Particle and continuum methods
1.Atoms, molecules, chemistry 2.Continuum modeling approaches and solution approaches 3.Statistical mechanics 4.Molecular dynamics, Monte Carlo 5.Visualization and data analysis 6.Mechanical properties – application: how things fail (and how to prevent it) 7.Multi-scale modeling paradigm 8.Biological systems (simulation in biophysics) – how proteins work and how to model them
II. Quantum mechanical methods we are here
Welcome to Part 2!
The next 11 lectures will cover atomistic quantum modeling of materials.
Note: there will be a substitute lecturer on Tuesday,April 10 and no class on Thursday,April 12.
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Part II Topics 1. It’s a Quantum World:The Theory of Quantum Mechanics
2. Quantum Mechanics: Practice Makes Perfect
3. From Many-Body to Single-Particle; Quantum Modeling of Molecules
4. Application of Quantum Modeling of Molecules: Solar Thermal Fuels
5. Application of Quantum Modeling of Molecules: Hydrogen Storage
6. From Atoms to Solids
7. Quantum Modeling of Solids: Basic Properties
8. Advanced Prop. of Materials:What else can we do?
9. Application of Quantum Modeling of Solids: Solar Cells Part I
10. Application of Quantum Modeling of Solids: Solar Cells Part II
11. Application of Quantum Modeling of Solids: Nanotechnology
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Lesson outline
• Why quantum mechanics?
• Wave aspect of matter
• Interpretation
• The Schrödinger equation
• Simple examples
Courtesy of Bernd Thaller. Used with permission.4
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Engineering science paradigm: Multi-scale
view of materials
Buehler and Ackbarow, Materials Today, 2007
Multi-scale modeling
quantum
modeling
Courtesy of Elsevier, Inc., http://www.sciencedirect.com. Used with permission.5
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It’s a quantum world!
© Shizuo Kambayashi/AP. All rights reserved. This content is excluded from our CreativeCommons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.6
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Motivation
If we understand electrons,then we understand everything.
(almost) ...
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Quantum modeling/simulation
?
??
mechanical
properties
electricalproperties
optical
properties
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A simple iron atom ...
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Why Quantum Mechanics?Accurate/predictive structural/atomistic properties, when we need to span a wide range of coordinations, and bond-breaking, bond-forming takes place.(But beware of accurate energetics with poor statistics !)
EDIP Si potential Tight-binding © source unknown. All rights reserved. This content is excluded from our Creative Commons license. For more information, see http://ocw.mit.edu/fairuse.
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Electronic, optical, magnetic properties
Jahn-Teller effect in Non-resonant Raman in silicates (Lazzeri and Mauri)
porphyrins (A. Ghosh)
Image removed due to copyright restrictions. Please seeVangberg, T. R. Lie, and A. Ghosh. "Symmetry-BreakingPhenomena in Metalloporphyrn in Pi-Cation Radicals."
Courtesy of Elsevier, Inc., http://www.sciencedirect.com. Used with permission.
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Reactions
1,3-butadiene + ethylene → cyclohexene
See Lecture 1 video for animation. © James E. Kendall/MSC Caltech. All rights reserved. This content is excludedfrom our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.12
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Standard Model of Matter
•Atoms are made by MASSIVE, POINT-LIKE NUCLEI (protons+neutrons)
•Surrounded by tightly bound, rigid shells of CORE ELECTRONS
•Bound together by a glue of VALENCE ELECTRONS (gas vs. atomic orbitals)
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It’s real!
Cu-O Bond Ti-O Bond(experiment) (theory)
Reprinted by permission from Macmillan Publishers Ltd: Nature. Source:Zuo, J., M. Kim, et al. "Direct Observation of d-orbital Holes and Cu-CuBonding in Cu2O." Nature 401, no 6748 (1999): 49-52. © 1999.14
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Importance of Solving for this Picture with a Computer
• It provides us microscopic understanding• It has predictive power (it is “first-principles”)• It allows controlled “gedanken” experiments• Challenges:‣Length scales‣Time scales‣Accuracy
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Why quantum mechanics?
Classical mechanics
d(m⌃v)Newton’s laws (1687) F⌃ =
dt
Problems?
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Why quantum mechanics?
Problems in classical physics thatled to quantum mechanics:
• “classical atom”
• quantization of properties
• wave aspect of matter
(black-body radiation), ...•17
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Quantum mechanists
Werner Heisenberg, Max Planck,Louis de Broglie, Albert Einstein,Niels Bohr, Erwin Schrödinger,Max Born, John von Neumann,
Paul Dirac, Wolfgang Pauli(1900 - 1930)
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“Classical atoms”
problem:accelerated charge causes radiation, atom is not stable!
+
e-
hydrogen atom
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Quantization of propertiesphotoelectric
effect
E = �(⇥ � ⇥A) = h(� � �A)
h = 2�� = 6.6 · 10�34 Wattsec.2
Einstein: photon E = ��
Ee
��A
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__ _ _
__
_ _
____
_
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Quantization of properties
atomicspectra
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Quantization of propertiesEn
ergy
E = ��
possibleenergystates
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The Double-Slit Experiment
Dr Quantum explains the double-slit experiment. From the film: What the bleep do we know?
See Lecture 1 video for full clip.
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"Anyone who is not shocked by quantum theory has not
understood it"
Niels Bohr
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Schrödinger’s Cat
ErwinSchrödinger
(1887 – 1961)
"I don't like it, and I'm sorry I ever had anything to do with it," Schrödinger, on the cat paradox.
Courtesy of Dan Lurie on Flickr. License: CC-BY-NC-SA.
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EPR ParadoxEinstein–Podolsky–Rosen
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Wave-Particle Duality•Waves have particle-like properties:
•Photoelectric effect: quanta (photons) are
exchanged discretely
•Energy spectrum of an incandescent body
looks like a gas of very hot particles
•Particles have wave-like properties:
•Electrons in an atom are like standing waves (harmonics) in an organ pipe
•Electrons beams can be diffracted, and we can see the fringes
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Interference Patterns
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Wave Interactions
+-
A1
A2
Resultant A1+ A2 Resultant A1- A2
Constructive Interference Destructive Interference
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Interference Patterns
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Bucky- and soccer balls
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When is a particle like a wave?
Wavelengths:
Electron: 10-10 mC60 Fullerene: 10-12 mBaseball: 10-34 mHuman wavelength: 10-35 m
20 orders of magnitude smaller than the diameter of the nucleus of an atom!31
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Classical vs. quantum
It is the mechanics of waves rather than classical particles.
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Wave aspect of matter
wave character particle character
lightmatter
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_ _
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_
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Mechanics of a Particle
€
d2rm 2 = F(r) r(t) v(t)dt
€ €
The sum of the kinetic and potential energy is conserved.
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mMvV
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Description of a Wave
The wave is an excitation (a vibration): We need to know the amplitude of the excitation at every point and at every instant
Ψ =Ψ(r, t)
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Mechanics of a Wave
Ψ
(r, t) = Aexp[i(k • r −ωt)]Free particle, with an assigned momentum:
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Wave aspect of matterparticle: and momentum E ⇥p
� ⇥kwave: frequency and wavevector
E = h� = �⇥
⇧p = �⇧k =h
�
⇧k
|⇧k|
de Broglie: free particle can be described as planewave with � =
h
mv�(⌥r, t) = Aei(⌃k·⌃r��t)
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How do we describe the physical behavior of particles as waves?
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The Schrödinger equation
second derivative in spacea wave equation:
first derivative in time
H = ��2
2m⇥2 + V ( r, t) =
=p2
2m+ V = T + V
��
�2
2m⇥2 + V ( r, t)
⇥�( r, t) = i�
⇤
⇤t�( r, t)
Hamiltonian⇤p = �i�⇥
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In practice ...H time independent: �(⌃r, t) = �(⌃r) · f(t)
i�f(t)f(t)
=H�(�r)�(�r)
= const. = E
�(⌃r, t) = �(⌃r) · e� i� EtH�(⇧r) = E�(⇧r)
time independent Schrödinger equationstationary Schrödinger equation
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Particle in a boxSchrödinger equation
general solutionboundary conditions
Boundary conditions cause quantization!41
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Particle in a boxquantization
normalization
solution
Image adapted from Wikimedia Commons,http://commons.wikimedia.org.
42quantum number
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Simple exampleselectron in square well
electron in hydrogen atom
?
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Image adapted from Wikimedia Commons, http://commons.wikimedia.org.
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Harmonic oscillator
solve Schrödingerequation
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Harmonic oscillator
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Ψ3
Ψ2
Ψ1
Ψ32
Ψ22
Ψ12
Ψ02Ψ0
n=3
n=2
n=1
n=0
hω72
hω52
hω32
hω12
α x
Graphs of the quantum harmonic oscillator potential and wavefunctions.
Classical limits
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Interpretation of a wavefunction 3/24/08 5:42 PMhoscom2.gif 512!342 pixels
Page 1 of 1http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/imgqua/hoscom2.gif
3/24/08 5:42 PMhoscom2.gif 512!342 pixels
Page 1 of 1http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/imgqua/hoscom2.gif
|�|2 = ��� interpretation as probability to find particle (that is, if a measurement is made)
�(⇧r, t) wave function (complex)
� ⇤
�⇤��⇥dV = 1
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Connection to reality?
potential: 1/r
+
e-
hydrogen atom
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Many Interpretations of Quantum Mechanics!
Source: Wikipedia
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Summary
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Review
• Why quantum mechanics?
• Wave aspect of matter
• Interpretation
• The Schrödinger equation
• Simple examples
Courtesy of Bernd Thaller. Used with permission.50
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• Greiner, Quantum Mechanics:An Introduction
• Thaller, Visual Quantum Mechanics
• Feynman, The Feynman Lectureson Physics
• wikipedia, “quantum mechanics”, “Hamiltonian operator”,“Schrödinger equation”, ...
Literature
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MIT OpenCourseWarehttp://ocw.mit.edu
3.021J / 1.021J / 10.333J / 18.361J / 22.00J Introduction to Modelling and SimulationSpring 2012 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.