PG510

Symmetry and Molecular Spectroscopy

Lecture no. 1 Group Theory: Definitions and Theorems Giuseppe Pileio
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Introduction to the course

About Me

Name: Giuseppe Surname: Pileio Nickname: Peppe Location: 30/3047, School of Chemistry E-mail: g.pileio@soton.ac.uk Phone: 023 80 59 4146 Web: http://www.mhl.soton.ac.uk/~peppe
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About You ! Fill Form A with your details and past experiences ! Use Form B throughout the course to annotate crucial sentences ! Use Form C throughout the course to give me comments and feedbacks on your understanding level ! Keep the molecular model in the envelope for the full duration of the course. It will help you in understanding ! Finally, note that to get the 12 credits only attendance to all the lectures and workshops is needed. No exams required!
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Course plan: Overview Group Theory Symmetry Operations Symmetry Groups

Molecular Spectroscopy

Vibra

tiona l IR

Raman IR and MW

Course plan details: Part I

Part I: Group Theory (5 lectures + 1 workshop)

1- Group Theory 2- Molecular Symmetry 3- Point Groups 4- Representations of groups 5- Character tables
Workshop 1 (group theory and molecular symmetry)
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Course plan details: Part II

Part II: Molecular Spectroscopy (7 lectures + 2 workshops)

6- Introduction to spectroscopy 7- Rotational, Vibrational and Vibro-rotational Spectroscopy 8- Vibrational Spectroscopy of polyatomic molecules 9- Raman Spectroscopy
Workshop 2 (about Rotational, Vibrational and Raman Spectroscopy)

10-12 Electronic Spectroscopy

Workshop 3 (about MO and Electronic Spectroscopy)
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Plan of action Lectures are introductory to the subject and medium -level. Only basic math is required. Quantum mechanics concepts have been avoided as much as possible and when present a deep understanding is not required Workshops are intended as an application of these concepts. Most likely an exercise will be done by me on the board and some others by you (working in groups and with my help). Those papers will not be marked although I will correct them A molecular model is given to you to be used throughout the course (bring it to all lectures and workshops). Very simple tasks on that will be asked as homework
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Crucial concepts will be highlight and collected by you in Form B as an useful reminder (bring it to all lectures and workshops) Form A is intended to help me in understanding your starting level and your knowledge on the subject in order to better meet your requirements Form C (one for each lecture) is intended to help me to figure out your understanding level of the concepts discussed so to, eventually, come back to these concept in a clearer way or address them in other circumstances
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textbooks
Introductive:

Molecular Spectroscopy (Oxford Chemistry Primers), J. M. Brown, ISBN 978-0198557852 Foundation of Spectroscopy (Oxford Chemistry Primers), S. Duckett and B. Gilbert, ISBN 978-0198503354
Fundamental:

Chemical Applications of Group Theory, F. A. Cotton (3rd ed.), ISBN 9971-51-267-X

Deeper Understanding:

Symmetry and Spectroscopy D. C. Harris and M. D. Bertolucci, ISBN 0-486-66144-X

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Overall Learning Outcomes By the end of this course you will be able to: !! Understand the fundamentals of Group Theory and apply it to molecular spectroscopy !! Understand the link between molecular spectroscopy, symmetry and information content of molecular spectra !! Calculate/predict energy levels and spectral features using symmetry as a simplification tool !! Use symmetry arguments to possibly solve molecular problems
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Lecture no. 1

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Groups What is a group? A Group is a collections of elements that follow these rules: 1.! The combination of any two elements of the group is itself a member of the group A * B = C and C belongs to the same group as A and B 2.! One element must commute with all the others leaving them unchanged E*A=A*E=A This element, E is usually called identity element
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3.! Combination must be associative A * (B *C) = (A * B) * C 4.! Every element must have a reciprocal which is still an element of the same group A*X=X*A=E ! A, X and E belong to the same group (rule 1) ! If X is the reciprocal of A then A is the reciprocal of X ! E is the reciprocal of itself i.e. E * E = E ! (A * B ** Z)-1 = Z-1 ** B-1 * A-1
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Abelian Groups If a 5th rule is also fulfilled we call the group Abelian Group or Commutative Group: 5.! The combination of two element is commutative A*B =B*A Note: Although very common in many everyday mathematical applications this rule generally does not hold in Group Theory!
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Properties of Groups ! ! The number of element in the group is called order and is indicated by h Smaller group found in a group are called subgroups and their order is indicated with g so that h/g=k with k an integer A group is called Cyclic if it is made by only one element and its h powers In the simplest h=3 group (G3): A A*A=B A*A*A=A*B=E

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Similarity Transformations A similarity transformation is present if A and X are both elements of the group G and B = X-1 * A * X with B being another element of G (rule 1). In words we say: B is the similar transform of A by X or A and B are conjugate
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Properties of conjugation ! Every element is conjugate with itself A = X-1 * A * X ! If A is conjugate with B then B is conjugate with A A = X-1 * B * X B = Y-1 * A * Y ! with Y = X-1 and Y-1 =X

If A is conjugate with B and C then B and C are also conjugate with each other if Then A = X-1 * B * X and A = Y-1 * C * Y
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B = Z-1 * C * Z

Classes of elements A complete set of elements that are conjugate to one another is called a class of the group

To figure out all the classes within a group we have to take every element of the group and work out the similarity transform with all the other element. The elements conjugate each other will form a class

The order of each class must be integer factor of h and their sum must be h
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Examples of Groups: The Integers with respect to + Lets take the collection of all the integers and lets choose the sum (+) as a rule for the combination of these elements. Do they form a group? Rule 1 is satisfied since the sum of any two integers give another integer i.e. another element of the group Rule 2 is satisfied if we choose 0 as identity: 0 + k = k + 0 = k (with k any integer) Rule 3 holds since the sum is obviously associative Rule 4 is satisfied if we choose k as the reciprocal of any element k since: k + (-k) = 0 The group is also Abelian since the sum is commutative
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Examples of Groups: The Integers with respect to x Lets take the integers again but choose the simple product (x) as a rule for the combination. Do they still form a group? Rule 1 is satisfied since the product of any two integers give another integer i.e. another element of the group Rule 2 is satisfied if we choose 1 as identity: 1 x k = k x 1 = k (with k any integer) Rule 3 holds since the product is obviously associative Rule 4 is satisfied if we choose 1/k as the reciprocal of any element k since: k x (1/k) = 1 The group is also Abelian since x is commutative
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What did we learn in this lecture?

! The concept of group ! The rules that make a collection of elements be a group ! Some properties of groups ! The concept of similarity transform and its properties ! The concept of class ! Examples of groups
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