CH354S / CH393L – Elements of Spectroscopy

Electronic & Vibrational Spectroscopy of Molecules & Materials

Fall 2020, Unique 50245 / 50525

Class: Monday/Wednesday, 12:30 pm – 2:00 pm

Meeting online via Zoom ID: 933 5750 7645

Instructor: Dr. Sean T. Roberts, roberts@cm.utexas.edu

Office: WEL 3.120B (currently not on campus)
Pronouns: he, him, his

Office Hours: Tues. 2:00 – 3:00 pm, Fri. 12:00 noon – 1:00 pm, or by appointment
Office Hours Zoom ID: 940 2347 6075

Teaching Assistant: Jon Bender, jonbender@utexas.edu

Office: WEL 3.142 (currently not on campus)
Pronouns: he/they, him/them

TA Office Hours: Wed. 2:00 – 3:00 pm, Thurs. 10:00 – 11:00 am; Zoom ID: 512 314 6188

Course Objectives: The interaction of light with matter forms the basis for several powerful
experimental methods employed by scientists and engineers in both research laboratories and
industrial settings to probe the structure and dynamics of molecules and materials. The goal of
this course is to provide you with an introduction to physical principles that govern light-matter
interactions and to build from them an intuitive understanding of common spectroscopic methods
used to probe the electronic and nuclear structure of molecules and materials such as
semiconductors and metals.
As a senior undergraduate/graduate course, emphasis will be placed on building a key
understanding of useful spectroscopic tools that you can apply to problems that you encounter in
an academic lab or industrial setting. Developing your skills for both scientific writing and oral
communication are also goals of this course as they can enhance your ability for success as you
progress through your careers.

Prerequisites: CH354S: CH 353 or 353M, CH 354 or 354L, or consent of instructor.

CH393L: graduate standing or consent of instructor
The prerequisites above are to ensure you possess a sufficient background in time-independent
quantum mechanics, mathematics, and fundamental physics needed to tackle concepts covered
by this course. I will do my best to provide a refresher to key background material concepts, but
any refresher provided will by no means be exhaustive. If we cover a topic that relies on a
foundational concept you’re unfamiliar with, I encourage you to contact me outside of class. I am
happy to recommend resources that address any foundational topic.

Suggested Textbooks: Given the breadth of material covered by our course, no single textbook
provides a comprehensive description of every topic that we will cover. In composing my lectures,
I have drawn on several sources listed below. As we move through course material, I’ll post
suggested readings from these texts and other resources.

I have used the following texts for developing my notes for the course:
• “Symmetry & Spectroscopy: An Introduction to Vibrational and Electronic Spectroscopy”
by Daniel C. Harris & Michael D. Bertolucci: Delves into electronic and vibrational
Elements of Spectroscopy Dr. Sean Roberts
CH 354S / CH 393L Fall 2020

spectroscopy from the point of view of group theory, which is used to determine selection
rules. An excellent text. Also available from Dover at a reasonable price.
• “Principles of Molecular Photochemistry: An Introduction” by Nicholas J. Turro: Wonderful
text that introduces the photophysics of organic molecules. The first 2 chapters introduce
concepts commonly touched on in time-resolved electronic spectroscopy.
• “Introductory Nanoscience: Physical and Chemical Concepts” by Masaru (Ken) Kuno:
Fantastic text that discusses light-matter interactions and the electronic structure and
spectroscopy of both bulk and nanoscale semiconductors and metals. A great reference
for sorting through the various units scientists use for reporting spectroscopic observables.
• “Molecular Spectroscopy” by Jeanne L. McHale: Ch. 1 - 3 provide a good overview of core
quantum mechanics and electrodynamics principles covered in foundational courses. Ch.
4 develops time-dependent perturbation theory. Ch. 9 – 12 cover molecular spectroscopy.
• “Time-dependent Quantum Mechanics and Spectroscopy” by Andrei Tokmakoff (Online
textbook, tdqms.uchicago.edu): Gives a beautiful overview of time-dependent perturbation
theory and its application to time-resolved spectroscopy that is mathematically rigorous
yet highly approachable. We’ll cover several topics detailed by Andrei in his notes.
• “Solids and Surfaces: A Chemist’s View of Bonding in Extended Structures” by Roald
Hoffman: Provides a beautiful view of band structure built up in real space based on
chemical bonding principles. Required reading for anyone doing solid-state chemistry.
Other key texts that contain topics we’ll touch on include:
• “Introduction to Quantum Mechanics: 2nd Edition” by David J. Griffiths: Introduces quantum
mechanical concepts at a level that is a bit more advanced than many undergraduate
texts, but not quite at the level of many graduate texts. Verbose, but easy to read.
• “The Physics of Low Dimensional Semiconductors” by John H. Davies: Provides a review
of quantum mechanics and an introduction to solid state physics concepts such as band
structure from a physical point of view using Bloch functions.
• “Quantum Mechanics in Chemistry” by George C. Schatz & Mark A. Ratner: Provides an
alternative take on some topics we’ll cover this semester related to time-dependent
quantum mechanics. It’s also available from Dover at a reasonable price.

Piazza: We will be using Piazza for nearly all online activity for the course:
piazza.com/utexas/fall2020/ch354sch393l
Piazza provides a wonderful discussion board complete with a LaTeX editor for equation
integration. Questions posted to Piazza will regularly be answered by Jon and myself. Lecture
notes, problem sets, videos, and other course resources will be made available via Piazza.
Please check Piazza regularly! Announcements relevant to homework and other course logistics
will be posted as well as periodic class polls.

Canvas: Canvas will only be used for grade distribution. All other course information will be
posted to Piazza. Messages posted to Canvas will not receive a speedy reply from Jon or myself.

Email Policy: Questions regarding the course material or logistics should be posted to Piazza
and not to me via personal email. I consider such questions to be public and will ask you to repost
them to Piazza so your colleagues can benefit from the discussion.

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Elements of Spectroscopy Dr. Sean Roberts
CH 354S / CH 393L Fall 2020

Questions that pertain to your specific situation in the course, such as missing a class lecture or
issues tied to course enrollment, can be submitted to me via email.

Class Meetings: All scheduled class meetings (lectures, office hours) will occur virtually via
Zoom. The course Piazza webpage contains links to all scheduled Zoom meetings.
On occasion, we will break into groups during class to complete some short exercises. Written
exercises will be collected by submitting a PDF, which can be produced using a cell phone camera
or other scanner technology. Please assess your ability to generate PDFs of written work.
If you need aid to secure technology to meet any aspect of the course, please contact me directly.

Lecture Notes: My lectures will entail notes that I hand write during class and display using the
document camera. These notes will be posted to the course website after each class. I will also
post a brief summary that identifies the key concepts of the material covered in class each day.
Context for understanding these notes is critical and I encourage you to take your own notes
during class to supplement these materials.
I also encourage you to ask questions during class. If you are having trouble understanding a
concept, I guarantee you’re not the only one in the room with that question.

Problem Sets: Four problem sets will be given out over the course of the semester and you will
have at least two weeks to complete each. These sets are designed to both aid you in internalizing
the abstract concepts seen in lecture and to develop the ability to apply these concepts to
chemical and material systems of interest.
This course places a strong emphasis on both fundamental concepts that underlie spectroscopic
lineshapes and their practical application to chemical and material systems. Often, the electronic
and vibrational structure of even relatively simple molecules can be quite complicated, leading to
congested spectra with several overlapping transitions. As such, developing skills in both
numerical computation and the fitting of spectral lineshapes is key to being able to maximally
extract chemical information from lineshapes.
The problems sets are designed with this skill emphasis in mind. Problems will, on occasion,
require use of software capable of numerical integration/differentiation, peak fitting, and other
related operations. UT Austin provides free access to software such as Matlab and Mathematica
that can meet these demands. Personally, I have a lot of experience using Matlab and can better
assist with debugging code written in that language. I encourage you to form study groups and to
work together on the problem sets. If you do work in groups, note down who you collaborate with,
but be sure to compose your own set of solutions to each problem set.

Class Project: Rather than a final exam, you will be tasked with completing a research paper on
a topic that is of relevance to material covered in the course (and for graduate students, ideally
your PhD research). This paper can consist of calculations of spectroscopic signals, a
comprehensive review of a set of spectroscopic techniques, an analysis of spectroscopic data
you’ve managed to produce in lab, or other topics of interest to you that have relevance to both
spectroscopy and your future career goals.
Your research paper should be succinct (no more than ~4000 words excluding abstract,
references, and figure captions) and formatted in a style appropriate for publication in a chemistry
journal. This involves inclusion of an abstract (< 250 words), appropriate references, figures
embedded in the text, and a table of contents figure that summarizes your project’s key points.

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Elements of Spectroscopy Dr. Sean Roberts
CH 354S / CH 393L Fall 2020

I encourage you to discuss with me potential topics for your paper early in the semester to make
sure they are of an appropriate scope for a project. You are required to submit a one-paragraph
abstract describing your chosen topic to me by Friday, September 18th. I will provide you with
feedback on your abstract shortly after receiving it and you will be allowed to revise it if its scope
and/or focus is not appropriate for a class project.
As soon as your abstract is approved, you should commence work on your project. I will be happy
to review drafts of your project as you work to complete them, advise you in computational
approaches needed to meet goals of your project, or to aid you in locating key points of literature
needed to complete your project to the best of my abilities.
A complete draft of your paper suitable for review is due on Friday, October 23rd.
Following submission, each paper will have two students assigned to it who will write reviews due
the following week on Friday, October 30th. These reviews are meant to be akin to those you
would compose when engaging in peer review for a scientific journal. Your reviews should: (1)
signal a clear understanding of the paper’s topic to both the writer and “ journal editors” (i.e. Jon
and myself), (2) identify the paper’s strengths and weaknesses, and (3) provide constructive
criticism for how the paper can be improved. The reviews you compose will be evaluated as a
part of your final grade.
Following receipt of your reviews, you will have a chance to revise your project prior to Monday,
November 23rd, when its final draft is due
Dates listed above for the class project are hard deadlines. Late submissions will not be accepted
without a valid excuse.

Final Presentation: In addition to your written project, you will be asked to produce a 12 – 15
minute presentation summarizing the key results from your project. These presentations are
meant to be similar to research talks one may give at an ACS, MRS, or APS meeting and should
provide the audience with enough background information that they can follow the main
conclusions of the work before giving a concise description of the work’s main points and
conclusions.
Our final 3 class periods following Thanksgiving break will be dedicated to the evaluation of these
presentations. Your presentation should be recorded in either powerpoint, as an mp4 file, or other
easily sharable video format and uploaded to the course webpage so that all members of the
course can view the video. Each of these final 3 periods will have 5 – 6 students assigned to that
period and the class will serve as a Q & A session during which members of the course, Jon, and
I can ask questions regarding the presentation. Members of the class will be graded both on their
replies to questions and participation in the discussion.

Course Grades: Grades will be assigned based on your performance on homework assignments,
your class project, and the reviews you provide for the projects of your peers:
Problem Sets: 50% of grade
Class Project: 30% of grade (1 third initial draft, 2 thirds final version)
Project Reviews: 10% of grade
Class Presentation: 10% of grade
I intend to curve the class distribution at the end of the semester. However, rough guidelines for
evaluating your score throughout the semester are as follows:
A = 85% and above; B = 70 – 85%; C = 55 – 70%; D = 45 – 54%; F < 45%

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Elements of Spectroscopy Dr. Sean Roberts
CH 354S / CH 393L Fall 2020

Academic Integrity: Students must uphold UT Austin’s Honor Code: “The core values of The
University of Texas at Austin are learning, discovery, freedom, leadership, individual opportunity,
and responsibility. Each member of the university is expected to uphold these values through
integrity, honesty, trust, fairness, and respect toward peers and community.”
Academic dishonesty or any unfair academic advantage will not be tolerated.

Sharing of Course Materials is Prohibited: No materials used in this class, including, but not
limited to, lecture hand-outs/worksheets, videos, and assessments (papers, projects, homework
assignments), may be shared online or with anyone outside of the class unless you have my
explicit, written permission.

Class Recordings: Class recordings are reserved only for students in this class for educational
purposes and are protected under FERPA. The recordings should not be shared outside the class
in any form. Violation of this restriction by a student could lead to Student Misconduct
proceedings.

Online vs. In-person Meetings: While this course is listed as a “hybrid” format with both in-
person and online course content, the decision to designate our course in that manner was made
earlier in the summer when the status of COVID-19 during the fall was uncertain. Given current
infection rates in Austin and the surrounding area, I believe the best course of action is to hold
our course exclusively online during the early part of the fall and to monitor progress of the
pandemic to assess if in-person meetings are at some point permissible.
If that change is made, the syllabus will be updated well in advance of any changes to the course.
All course materials will also remain available online. Any student wishing to complete this course
fully online will be able to do so with no penalty to their grade.

Zoom Etiquette: Video: When attending class or office hours, I ask that you enable your video
so that Jon, I, and other members of the class can see you. I believe this makes our classroom
environment more welcoming and will aid in facilitating discussion. If this makes your internet
connection unstable, its fine to disable your video. Likewise, if you do not feel comfortable sharing
your video, it is ok to turn it off occasionally to give yourself a break.
Audio: Please keep your audio on mute until you want to speak. If you have a question during
large class discussions, please use the “raise hand” feature in Zoom to indicate you have an idea
you want to share.
Zoom Recordings: Lastly, I will record class meetings, but not office hours. However, you should
do your best to make class meetings to participate in small group exercises. You should also be
prepared to take notes during class as this can help you to internalize the course material.

Students with Disabilities: Please notify me of any modification/adaptation you may require to
accommodate a disability-related need. You will be requested to provide documentation to the
Dean of Students' office, in order that the most appropriate accommodations can be determined.
Specialized services are available on campus through Services for Students with Disabilities.

COVID Monitoring: To help keep everyone at UT and in our community safe, it is critical that
students report COVID-19 symptoms and testing, regardless of test results, to University Health
Services, and faculty and staff report to the HealthPoint Occupational Health Program (OHP) as
soon as possible. Please see this link to understand what needs to be reported. In addition, to
help understand what to do if a fellow student in the class (or Jon or I) tests positive for COVID,
see this University Health Services link.

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Elements of Spectroscopy Dr. Sean Roberts
CH 354S / CH 393L Fall 2020

Course Schedule: Below, I’ve listed my current plan for the scheduling of class events. Problem
Sets will be given out roughly every ~2 weeks during the early portion of the semester and you’ll
have ~2 weeks to complete them. While due dates for Problem Sets may move, I am not planning
on moving dates tied to the class project.
If we near the end of the semester and are running out of time to cover key topics, I am happy to
schedule additional class meetings (if the class wishes) to cover topics of interest.

Week Date Event Notes Week Date Event Notes

1 26-Aug Lecture 1 19-Oct Lecture 15 nanoGe Conference
31-Aug Lecture 2 9 21-Oct Lecture 16 nanoGe Conference
2
2-Sept Lecture 3 Friday, Oct 23 Project Drafts Due
7-Sept No Class Labor Day 26-Oct Lecture 17
3 9-Sept Lecture 4 10 28-Oct Lecture 18
Friday, Sept 11 Problem Set 1 Due Friday, Oct 30 Project Reviews Due
14-Sept Lecture 5 2-Nov Lecture 19
11
4 16-Sept Lecture 6 4-Nov Lecture 20
Friday, Sept 18 Project Abstracts Due 9-Nov Lecture 21 Problem Set 4 Due
12
21-Sept Lecture 7 11-Nov Lecture 22
5 23-Sept Lecture 8 Abstract Feedback 16-Nov Lecture 23
13
Friday, Sept 25 Problem Set 2 Due 18-Nov Lecture 24
28-Sept Lecture 9 23-Nov Lecture 25 Final Project Due
6 14
30-Sept Lecture 10 25-Nov No Class Thanksgiving
5-Oct Lecture 11 NSF Review Panel 30-Nov Final Presentations: Group 1
15
7 7-Oct Lecture 12 2-Dec Final Presentations: Group 2
Friday, Oct 9 Problem Set 3 Due 16 7-Dec Final Presentations: Group 3
12-Oct Lecture 13
8
14-Oct Lecture 14

Course Overview: So what is this course all about…?

The interaction of light with matter is perhaps one of the most important tools that chemists have
available for determining the structure of molecules and materials. The visible color of compounds
is dictated by the arrangement of electrons within them while techniques such as infrared
absorption and light scattering are sensitive reporters of the arrangement of nuclei within a
compound. Moreover, by manipulating the chemical structure of a material, its light absorption
and emission properties can be readily changed, which has enabled design of numerous chemical
labels and sensors, light emitting devices, photocatalytic systems, and other light-driven
applications.
However, predicting how light interacts with a given compound is complicated by the fact that the
electrons and nuclei which comprise a compound are all low mass particles, which means that
their behavior is dictated by quantum mechanics. As such, we need to understand how quantum
mechanical structures respond to time-evolving external stimuli such as light. In principle, we can
turn to the time-dependent Schrodinger equation for guidance on this point. Solving this equation
in practice, however, for any systems with a high degree of complexity quickly becomes incredibly
challenging. Fortunately, a series of approximation methods exist for tackling this problem.
Exploring these methods, in particular time-dependent perturbation theory and its application to
light-matter interactions, will be our first key goal for this semester.

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Elements of Spectroscopy Dr. Sean Roberts
CH 354S / CH 393L Fall 2020

With that framework established, we can then apply it to a variety of different chemical compounds
to predict how their structure influences the colors of light that they absorb and emit. We’ll find
that light’s nature as an oscillating electric field dictates that only certain types of electron and
nuclear motion can effectively couple to a radiation field and hence exchange energy with it. This
will lead to a series of “selection rules” that dictate which quantum states within a molecule can
be linked by light and which cannot. We’ll see that these rules are often dictated by the underlying
symmetry of a molecule, which can give rise to characteristic patterns of light absorption/emission
that can be analyzed to infer its structure.
Just as spectroscopic absorption and emission lineshapes of small molecules are related to their
structure, so too are the absorption and emission lineshapes of materials such as semiconductors
and metals. Spectra of these extended covalent systems are often sensitive to their size. For
example, gold atoms absorb discrete frequencies of light, small gold particles are reddish in color,
absorbing broadly in the visible range, while bulk gold is a reflective yellowish solid. How each of
these gold structures interact with light reflects how their electrons are arranged within them. We’ll
close the semester by discussing how principles we develop for describing how molecules interact
with light can equally be applied to extended solids such as semiconductors and metals.

Topics to be Covered: Below, I’ve provided a rough list of topics I hope to cover this semester.
I say “hope” as this is my first semester teaching this course, so I do not have a full grasp for how
much time will be needed to cover each topic to a sufficient level of detail. Some topics listed
below may be skipped as the semester moves along to reach other ones of greater importance.
With that said, this course has the goal of building your understanding of spectroscopy, not mine.
As such, towards the latter half of the semester I am happy to focus more on topics the class is
interested in rather than continuing down the list below in linear order.

To be Covered in Order
1) Spectroscopy Fundamentals
• Quantum Mechanics Background
o Time-independent & Time-dependent Schrödinger Equation
o Separation of Variables
o Time-dependent Perturbation Theory
o Fermi’s Golden Rule
• Light-matter Interactions
o Light-matter Interaction Hamiltonian
o Rotating Wave and Dipole Approximations
o Absorption, Stimulated & Spontaneous Emission
2) Spectroscopy of Molecular Systems
• Vibrational Spectroscopy
o Quantum Harmonic Oscillator & Selection Rules
o Determining Normal Modes & Mode Symmetry
o Anharmonic Effects (Fermi Resonances, etc.)
o IR vs. Raman Spectroscopy
• Electronic Spectroscopy
o The Born-Oppenheimer Approximation
o Displaced Harmonic Oscillator Model for Absorption/Emission
o MO Theory & Selection Rules based on Orbital Symmetry
o Role of Electron Spin in Organic Systems
o Electronic Coupling & Molecular Aggregates

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Elements of Spectroscopy Dr. Sean Roberts
CH 354S / CH 393L Fall 2020

o Line Broadening Effects (Homogeneous vs. Inhomogeneous Lineshapes)

o Photoelectron Spectroscopy
3) Spectroscopy of Materials
• Organometallic Complexes
o Quick Review of Crystal Field Theory
o Electronic and Vibrational Spectroscopy
• Semiconductors & Metals
o A Chemist’s View of Band Structure as an Extension of MO Theory
o Bloch Theorem & Reciprocal Space
o Semiconductor Selection Rules (Direct vs. Indirect Transitions)
o Fermi-Dirac Distribution
o Density of States and Joint Density of States for Absorption/Emission
o Quantum Confinement (Quantum Dots, Wells, Sheets) & Selection Rules

Additional Topics to Be Covered as Time Permits

4) Models for Describing Energy & Charge Transfer
• Förster Resonance Energy Transfer
• Dexter Energy Transfer & Superexchange
• Marcus Theory of Electron Transfer
5) Spectroscopy of Free-electron Systems
• Drude & Sommerfield Models
• Plasmons & Localized Surface Plasmons
6) Spectroscopy of Electron Spins
• Spin Hamiltonians for Multi-electron Systems
• Electron Paramagnetic Resonance (EPR)
• Time-resolved Methods

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