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    Symmetry Exercises

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    Fei Pu
    This document contains solutions to homework problems from a chemistry 104a class on group theory. In problem 1, several sets and operations are tested to see if they form a group. Multiplication of positive integers and complex numbers form groups, while multiplication of negative integers does not due to lack of an identity element. In problem 2, the symmetry elements of various naphthalene derivatives are identified and illustrated. Their point groups are determined to be D2h, C2v, C2h, and Cs. Problem 3 assigns point groups to Sn molecules based on their geometries. Problem 4 is not shown but will be on a future solutions set. Problem 5 explores how changing ligands affects the point group. Problem 6 shows the character

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    Symmetry Exercises

    Uploaded by

    Fei Pu
    154 views8 pages
    This document contains solutions to homework problems from a chemistry 104a class on group theory. In problem 1, several sets and operations are tested to see if they form a group. Multiplication of positive integers and complex numbers form groups, while multiplication of negative integers does not due to lack of an identity element. In problem 2, the symmetry elements of various naphthalene derivatives are identified and illustrated. Their point groups are determined to be D2h, C2v, C2h, and Cs. Problem 3 assigns point groups to Sn molecules based on their geometries. Problem 4 is not shown but will be on a future solutions set. Problem 5 explores how changing ligands affects the point group. Problem 6 shows the character

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    Understanding symmetry

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    This document contains solutions to homework problems from a chemistry 104a class on group theory. In problem 1, several sets and operations are tested to see if they form a group. Multiplication of positive integers and complex numbers form groups, while multiplication of negative integers does not due to lack of an identity element. In problem 2, the symmetry elements of various naphthalene derivatives are identified and illustrated. Their point groups are determined to be D2h, C2v, C2h, and Cs. Problem 3 assigns point groups to Sn molecules based on their geometries. Problem 4 is not shown but will be on a future solutions set. Problem 5 explores how changing ligands affects the point group. Problem 6 shows the character

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    154 views8 pages

    Symmetry Exercises

    Uploaded by

    Fei Pu
    This document contains solutions to homework problems from a chemistry 104a class on group theory. In problem 1, several sets and operations are tested to see if they form a group. Multiplication of positive integers and complex numbers form groups, while multiplication of negative integers does not due to lack of an identity element. In problem 2, the symmetry elements of various naphthalene derivatives are identified and illustrated. Their point groups are determined to be D2h, C2v, C2h, and Cs. Problem 3 assigns point groups to Sn molecules based on their geometries. Problem 4 is not shown but will be on a future solutions set. Problem 5 explores how changing ligands affects the point group. Problem 6 shows the character

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    Chem 104a

    Homework 2 Solutions

    Fall 2011

    Problem Set 2 Solutions Chemistry 104a


    Problem 1
    Determine whether the following sets and operations form a group. Please briey explain your reasoning. (a) {all positive integers not equal to zero}, operation: multiplication

    Closure? Yes: Associativity? Yes: Identity? Inverse? Not a group. Yes: No:

    Multiplying 2 (+) integers gives a (+) integer. Multiplication of (+) integers satises the associative law A 1 = 1 A = A, for any positive integer A A A-1 = 1 - there is no A-1 in the integer set.

    (b) {all negative integers not equal to zero}, operation: multiplication

    Closure? No: Associativity? Yes: Identity? Inverse? Not a group. No: No:

    Multiplying 2 (-) integers gives a (+) integer. Multiplication of (-) integers satises the associative law Same as Closure. Theres no Identity element

    (c) {l, -l, i, -i, 0}, operation: multiplication

    Closure?

    Yes:

    Associativity? Yes: Identity? Yes: Inverse? No: Not a group.

    Product of two elements makes another (Make multiplication table) Complex numbers obey the associative law. 1 is the Identity element. No reciprocal for 0.

    Chem 104a

    Homework 2 Solutions

    Fall 2011

    (d) {E, C2 }, operation: successive application in Cartesian space.

    Closure?

    Yes:

    Associativity? Yes: Identity? Yes: Inverse? Yes: Yes, this is a group.

    E C2 E E C2 C2 C2 E Sequential E & C2 obeys the associative law. E is the Identity element. E E = E and C2 C2 = E

    Problem 2
    List all of the symmetry elements present for each molecule below. Make a sketch of each molecule and label each symmetry element. (a) Naphthalene

    E, C2 (C2 (z)), C2 (C2 (y)), C2 (C2 (x)), h ((xy)), v ((xz)), v ((yz)), i D2h

    Cl Cl (b) 1,8-Dichloronaphthalene Cl Cl

    Cl Cl

    Cl Cl E, C2 , v , v
    C2v (c) 1,5-Dichloronaphthalene

    Cl

    Cl Cl Cl

    Chem 104a

    Homework 2 Solutions

    Fall 2011

    Cl

    Cl Cl

    Cl

    Cl Cl Cl

    Cl
    E, C2 , h , i

    Cl
    (d) 1,2-Dichloronaphthalene

    C2h

    Cl Cl Cl

    E, h Cs

    Problem 3

    H Cl

    C Be

    N Cl

    Sketch and assign a point group to each of the following Sn molecules. The H Se H geometry about the central atom(s) is given in parantheses. Cl
    F F

    (a) Dichlorosilane SiH2 Cl2 (tetrahedral)

    Cl F

    Cl Si Cl H
    C2v

    Cl

    Cl

    (b) Beryllium chloride BeCl2 (linear)


    Cl P

    Cl Cl

    Fe

    Cl

    Si Cl Cl Si
    Chem 104a

    H H

    HF

    Cl F Cl

    Cl

    Cl Homework 2 Solutions H
    H Cl C N Cl

    H Cl Cl P H Cl Cl Sn H Cl P

    Cl

    Fall 2011
    Cl

    Fe Be
    DSe h
    F F

    (c) Hydrogen cyanide HCN (linear)

    Fe
    H Cl C Cl N

    HCl Cl Cl Cl F Cl H F Sn H Sn Cl

    Fe
    H H F H F F Cl H H Cl Cl

    Cv Cl Be Si Se N H H C Cl (d) Selenium diuoride SeF2 (angular) H F F


    Cl Be Cl

    Fe
    F

    Se

    Cl Fe C2v Si (e) Stibine SbH3 (trigonal pyramid) Cl H Cl Fe H


    Sb Si Fe

    F H Cl Cl F Cl Cl F P Cl Cl F Cl Cl Cl Cl

    Cl H
    C3v
    F Sb P

    H H H H H H

    Cl

    P Cl Cl P Cl

    Cl Cl Cl

    (f) Fluorophosphine PH2 F (trigonal pyramid) Fe H Fe H H


    P H F

    Cl

    Fe H Cs

    (g) Chlorostannane H3 SnCl (tetrahedral) Fe Fe


    H Cl C Be Se N Cl H H Sn Sb

    Fe

    H Cl H F F H C3v H F F Cl P Fe H F (h) Chlorine triuoride ClF3 (T-shaped) H F Cl

    Si Cl H

    Fe H
    H Sb Cl H H P Sb H Cl H H H Cl PP H Cl H

    4
    H

    F H Cl F

    H Cl Chem 104a H

    H Sn

    Be Cl CSe N Homework H F Cl F Be Cl FH Se H F F Cl Cl F

    H 2 Solutions H Cl Sn C Cl N HF Cl Be Cl F ClSe F H Sn H

    Fall 2011

    C2v HF C FN Si N Cl H H FC Cl F H (i) Chloroacetylene ClCCH (linear) Be Cl Cl Cl Be Cl Cl H Si Se Cl H Cl H H Se H Cl F F Cl F Cv F H F Si H F H Cl Cl Cl (j) Cyclohexane (chair conformation)ClP Cl H Cl Cl Cl Cl P Cl Fe Si N H Si Cl C H H H H Cl Cl Cl D3d H Cl Be Cl Cl Fe H (k) Cyclohexane (boat conformation) Se H F Fe F

    H Cl H H Cl Sn Sn F Cl Cl F F Cl H Cl P Sn Cl H Cl Cl Cl Cl F Cl Cl P P Cl F Cl Cl Cl Cl Cl F H H Cl Cl F F

    Cl

    Fe Fe

    F Cl Cl

    CCl 2v Fe Fe Si (l) Ferrocene (Hint: 3 possible conformations - Staggered, Eclipsed, and H Cl H Cl Fe Intermediate) H

    Fe Fe
    Sb H H P Sb HF P H F H H PFe F H H F F H HH HH Sb Fe

    Cl

    Fe Fe Fe Fe D5d

    Cl Cl P Cl Cl

    Fe
    H

    Sb H D5h H Sb H H H 5P P H H H H

    Fe

    Cl Si Cl H
    H C Be Se F F F Cl N Cl Sn H H Cl F Cl H

    Cl

    Chem 104a
    Cl

    Homework 2 Solutions

    Cl P

    Fall 2011
    Cl Cl

    Fe Cl Si Cl
    (m) PCl5
    F

    Cl

    H H

    D5

    Cl

    Fe
    Cl Cl Cl P Cl Cl

    Fe

    D3h Fe

    Problem 4
    Answer will be shown on the Problem Set #3 solutions.
    Sb

    Fe

    H H P H F X H H

    Problem 5
    Heres the starting molecule:
    X X X M X X

    X M X X

    Fe
    X

    (a) removing one X


    Sb H H X X M X F X P H H H X X X M X X X M X X Z C 4v X X X M X X X X X

    (b) replacing one X with a dierent ligand Z 6


    X X M X X X X M X X M X X X X X M X Z X X

    X X X M X X X

    X X M X X X Homework 2 Solutions X M X X X X X M X X X X X M X Z X X X M X X X X

    Chem 104a

    Fall 2011 X
    X X M X X X X X

    X X X M X X

    X X

    C4v
    X X X X X X X

    X (c) removing two trans X X X X X M X

    X X M X Z X X M X X M X Z X X X

    Xs M
    M X

    X X

    D4h
    X X M X X

    X X

    X X

    X X (d) removing two cis Xs X M X Z

    X X X X M X X X X M X X X M

    C2v
    X M X X M X

    (e) removing three mutually adjacent Xs (all 3 beside each other)


    X X X

    C3v

    Problem 6
    I think its helpful to draw the molecule and label each outer atom with its own number.
    Cl (5) Cl (3) P Cl (4) Cl (2) Cl (1)

    D3h 7

    Chem 104a

    Homework 2 Solutions

    Fall 2011

    Labelling helps visualize successive symmetry operations such as h C3 = S3 . Each successive symmetry operation should obey the Closure rule for groups. D3h E C3 2 C3 C2 C2 C2 h S3 5 S3 v v v E E C3 2 C3 C2 C2 C2 h S3 5 S3 v v v C3 C3 2 C3 E C2 C2 C2 S3 5 S3 h v v v
    2 C3 2 C3 E C3 C2 C2 C2 5 S3 h S3 v v v

    C2 C2 C2 C2 E C3 2 C3 v v v h S3 5 S3

    C2 C2 C2 C2 2 C3 E C3 v v v 5 S3 h S3

    C2 C2 C2 C2 C3 2 C3 E v v v S3 5 S3 h

    h h S3 5 S3 v v v E C3 2 C3 C2 C2 C2

    S3 S3 5 S3 h v v v C3 2 C3 E C2 C2 C2

    5 S3 5 S3 h S3 v v v 2 C3 E C3 C2 C2 C2

    v v v v h S3 5 S3 C2 C2 C2 E C3 2 C3

    v v v v 5 S3 h S3 C2 C2 C2 2 C3 E C3

    v v v v S3 5 S3 h C2 C2 C2 C3 2 C3 E

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