Chemistry 362 - Physical Chemistry II

Fall 2007

COURSE INFORMATION

 

Instructor:          Dr. Jean M. Standard

Office:                Julian Hall 222A

Phone:               438-7700

email:                 standard@ilstu.edu

Office hours:     MR 3-5 PM or by appointment

 

Text: Either Physical Chemistry, Thomas Engel & Philip Reid, Pearson Education, Inc., San Francisco, CA, 2006, or Quantum Chemistry & Spectroscopy, Thomas Engel, Pearson Education, Inc., San Francisco, CA, 2006.

 

Course Web Page: http://www.che.ilstu.edu/standard/che362

 

Exams: Three hour exams plus a final exam will be given. Half of the final exam will cover material between Exam 3 and the end of the semester and half of the final exam will be cumulative.

 

Tentative Exam Dates:

Exam 1 - Monday, September 17

Exam 2 - Monday, October 15

Exam 3 - Friday, November 9

Final - Thursday, December 13, 1 PM

 

Projects: Three projects, worth 50 points each, will be assigned during the course of the semester. These assignments will provide a more in-depth focus on particular topics in quantum chemistry and spectroscopy. Some of the projects will include a computer-based portion in order to familiarize you with state-of-the-art software for performing quantum chemistry calculations. Information from the projects will be included on the exams.

 

Homework: Several homework assignments will be distributed throughout the semester, at an average rate of about one assignment per week. Homework will not be graded; however, questions similar to the homework will appear on the exams. Therefore, it is in your best interests to work the problems. Answers to homework problems will be posted on the course web site.

 

Grading: Grades will be assigned based on the following point totals:

 3 Projects (50 points each):     150
 3 Hour Exams (100 points each):   300
 Final Exam:     150
 Total Points:   600

The exams and projects will be graded on a curve, which will affect the final grading scale. The tentative grading scale is: A: 90 - 100%; B: 80 - 89%; C: 70 - 79%; D: 60 - 69%; and F: 59% and below.

 

 

 

COURSE OUTLINE

 

Chemistry 362 deals mainly with the application of quantum mechanics to chemical problems. We will focus on understanding atomic and molecular structure and properties as well as the theoretical foundations of a number of types of spectroscopy. Later in the semester we will discuss statistical thermodynamics, which provides the link between the microscopic world and the macroscopic world.

 

So why study quantum mechanics? Dirac put it rather well back in 1929:

 

".. in the consideration of atomic and molecular structure and ordinary chemical reactions it is, indeed, sufficiently accurate if one neglects the relative variation of mass with velocity and assumes only Coulomb forces between various electrons and atomic nuclei. The underlying physical laws necessary for the mathematical theory of a large part of physics and the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these laws leads to equations much too complicated to be soluble. It therefore becomes desirable that approximate practical methods of applying quantum mechanics should be developed, which can lead to an explanation of the main features of complex atomic systems without too much computation."

 

P. A. M. Dirac, Proc. Roy. Soc. A 123, 714 (1929).

 

 

                                    Topic                                                     QC&S*               PhysChm*

 

I. Beginnings of the Quantum Theory

         A. Origins of Quantum Theory                                         1.1-1.4                12.1-12.4

         B. Quantization and Duality                                              1.5-1.7                12.5-12.7

         C. Classical Wave Equation                                              2.1-2.3                13.1-13.3

 

 

II. Quantum Mechanics

         A. Schršdinger Equation                                                   2.4                      13.4

         B. Operators                                                                      2.5, 3.2               13.5, 14.2

         C. Eigenvalue Equations                                                    2.5                      13.5

         D. Wavefunctions                                                             2.6                      13.6

         E. Probability Interpretation                                              3.1                      14.1

         F. Measurement, Expectation Values                                 3.3, 3.4               14.3, 14.4

 

 

III. Quantum Mechanics Examples

         A. Free Particle                                                                  4.1                      15.1

         B. 1D Particle in a Box                                                     4.2, 5.3               15.2, 16.3

         C. 2D, 3D Particle in a Box, Degeneracy                          4.3                      15.3

         D. Tunneling                                                                     5.5-5.7                16.5-16.7

 

 

IV. Heisenberg Uncertainty Principle

         A. Commutation Relations                                                6.1-6.2                17.1-17.2

         B. Uncertainty Principle                                                    6.3                      17.3

         C. Connection to Standard Deviations                               6.4                      17.4

 

 

V. Introduction to Spectroscopy

         A. The Electromagnetic Spectrum                                     8.1                      19.1

         B. Transition Probabilities, Selection Rules                       8.1                      19.1

         C. Absorption and Emission                                             8.2                      19.2

 

 

VI. Molecular Vibrations and Rotations

         A. Harmonic Oscillator Model                                          7.1                      18.1

         B. Vibrational Spectra of Diatomics                                  8.3                      19.3

         C. Vibrational Spectra of Polyatomics                               8.4, 8.5               19.4, 19.5

         D. Raman Spectroscopy                                                    8.8                      19.8

         E. Angular momentum                                                      7.2-7.5                18.2-18.5

         F. Rigid Rotor Model                                                        8.6                      19.6

         G. Rotational Spectra of Diatomics                                   8.6                      19.6

         H. Rotational Spectra of Polyatomics                                ----                      ----

         I. Rotation-Vibration Spectra of Diatomics                       8.6                      19.6

 

 

VII. Atoms

         A. The Hydrogen Atom and Hydrogen-like Ion                9.1-9.5                20.1-20.5

         B. The Helium Atom                                                         10.1                    21.1

         C. Electron Spin                                                                10.2                    21.2

         D. Pauli Principle, Aufbau Principle                                  10.3, 10.5           21.3, 21.5

         E. Atomic Term Symbols                                                  10.7-10.10          21.7-21.10

         F. Atomic Spectroscopy                                                    11.1, 11.2           22.1, 22.2

 

 

VIII. Diatomic Molecules

         A. Born-Oppenheimer Approximation                              12.2                    23.2

         B. Hydrogen Molecule Ion                                               12.2-12.5            23.2-23.5

         C. LCAO-MO Approximation                                          12.3, 13.2           23.3, 24.2

         D. The Variation Method                                                  10.4, 13.2           21.4, 24.2

         E. Other Diatomic Molecules, Correlation Diagrams        13.3-13.8            24.3-24.8

 

 

IX. Electronic Spectroscopy

         A. Molecular Term Symbols of Diatomic Molecules        15.2                    26.2

         B. Electronic Spectra of Diatomic Molecules                    15.3                    26.3

         C. The Franck-Condon Principle                                      15.4                    26.4

         D. Electronic Spectra of Polyatomic Molecules                15.5-15.6            26.5-26.6

         E. Fluorescence and Phosphorescence                              15.7, 15.8           26.7, 26.8

 

 

X. Quantum Chemistry of Polyatomic Molecules

         A. Huckel Theory                                                              14.7                    25.7

         B. Localized Bonds; Hybridization                                   14.2-14.4            25.2-25.4

         C. Potential Energy Surfaces                                             16.2                    27.2

         D. Hartree-Fock Molecular Orbital Method                      16.3, 16.4           27.3, 27.4

         E. Computational Chemistry                                             16.8, 16.9           27.8, 27.9

 

 

XI. Statistical Thermodynamics

         A. Statistical Basics, Probability                                        ----                      30.1, 30.2

         B. Distribution Functions                                                  ----                      30.4-30.6           

         C. Microstates and Configurations                                    ----                      31.1

         D. The Boltzmann Distribution                                         ----                      31.2-31.5

         E. Ensembles and Partition Functions                               ----                      32.1-32.7

         F. Equipartition Theorem                                                  ----                      32.8

         G. Thermodynamic Properties                                          ----                      33.1-33.4

 

 

* QC&S refers to Quantum Chemistry & Spectroscopy; PhysChm refers to Physical Chemistry.

 

 

Exam Coverage:

Note that these are tentative listings of the topics to be covered on each exam. In the interest of time, either Section X or Section XI may be omitted.

 

Exam 1:           Sections I - IV

Exam 2:           Sections V, VI

Exam 3:           Sections VII, VIII

Final:               Sections IX - XI, plus previous material for the cumulative portion