CHEMISTRY 634

✿ This course is for 3 credits.

✿ Lecture: 2 × 75 min/week; TTh 11:10 - 12:25,
Room 2122
✿ Grades will be based on the homework (roughly
25%), term paper (15%), midterm and final exams
✿ Web site: http://www.chem.tamu.edu/rgroup/
hughbanks/courses/634/chem634.html

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 Tim Hughbanks

Office: Chemistry Building, Room 330

Office phone: 845-0215
Office Hrs: Tues. 2:00 - 4:00 PM
Other times are OK too!
e-mail: trh@mail.chem.tamu.edu

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 Required Books, etc.
C. Hammond, “The Basics of Crystallography and
Diffraction”; Oxford, 4th Edition.
Harris & Bertolucci, “Symmetry and Spectroscopy,
An Introduction to Vibrational and Electronic
Spectroscopy”, Dover.
A. F. Orchard, “Magnetochemistry” ,Oxford.
J. Iggo, “NMR Spectroscopy in Inorganic
Chemistry”, Oxford.
✿ Handouts, posted lecture outlines, and
reference materials will be necessary (see
reading list in syllabus) - download all you
see there!

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Two Covers

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 Prerequisites
• Undergraduate chemistry courses,
especially inorganic and physical chemistry
• Chem 673 important in several places
• In the handout section of the web page
there are short introductions to vectors,
matrices, and quantum mechanical
techniques (perturbation theory, spin
operators, etc.)
• I will often include background physical
derivations that you needn’t memorize, but
try to understand the physical content!

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 Good Undergraduate
Background Text
• Housecroft & Sharpe,
“Inorganic Chemistry”, 4th
Edition, Chapters 19 and 20.
• We cover much more, but
these chapters fill in almost
everything I haven’t done in
detail.

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 Other Notable books
Abragam & Bleaney Electron Paramagnetic Resonance of Transition Ions
Canet Nuclear Magnetic Resonance Concepts and Methods
Carrington & McLachlan Introduction to Magnetic Resonance
Cheetham & Day Solid-State Chemistry Techniques
Clegg Crystal Structure Determination
Cotton Chemical Applications of Group Theory, 3rd Edition
Drago Physical Methods for Chemists, 2nd Edition
Ebsworth, Rankin & Cradock Structural Methods in Inorganic Chemistry, 2nd Ed.
Friebolin Basic One-and Two-Dimensional NMR Spectroscopy
Keeler Understanding NMR Spectroscopy
Housecroft & Sharpe Inorganic Chemistry, 4th Ed.
Orton Electron Paramagnetic Resonance
Giacovazzo, et. all Fundamentals of Crystallography
Solomon & Lever, eds. Inorganic Electronic Structure and Spectroscopy,
Volume II

Some Chapters of Drago are available (zipped, password protected):

http://www.chem.tamu.edu/rgroup/dunbar/chem634.htm
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Radiation & Energies

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Plane and Space Groups

Symmetry of Crystals

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 References for this Topic
✿ Cotton, “Chemical Applications of Group
Theory”, Chapter 10.
✿ Burns & Glazer, “Space Groups for Solid State
Scientists”, 2nd Edition
✿ Dunbar lecture notes are especially complete for
this topic: http://www.chem.tamu.edu/rgroup/
dunbar/Chem634/chem634.htm
✿ Wikipedia article on wallpaper groups is
excellent: http://en.wikipedia.org/wiki/
Wallpaper_group

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 Burns &
Glazer
3rd Edition,
2013

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 1-D Symmetry
• Seven types
1. unit translation
2. parallel (or longitudinal) reflection
3. perpendicular (or transverse) reflection
4. 2-fold rotational axis (C2)
5. a combination of C2 and one mirror
6. glide reflection
7. combination of: 3, 4, 6

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 1-D Symmetry Operations
unit translation longitudinal reflection

transverse reflection 2-fold rotational axis (C2)

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 1-D Symmetry Operations
combination of C2 and glide reflection
both types of mirrors

combination of C2,
transverse mirror,
and glide

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Distortions in Mo4O6 Chains

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 Bravais Lattices
• Direct Lattice:
– A regular, periodic array of points with a spacing
commensurate with the unit cell dimensions. The
environment around each points in a lattice is
identical.
• In 3-D, the set of direct lattice points can be written as
(vectors): R = ta + ub + vc t,u,v integers
• V = volume of unit cell

V = a ⋅ (b × c ) =
b ⋅ (c × a ) = c ⋅ (a × b)

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 Plane Lattices
• Lattices are generated by translational
symmetry only. (“Lattice” is a highly
misused term!) R = ta + ub ; t,u integers
• Five Plane Lattices
– Oblique, a, b, γ
– Rectangular - primitive and centered
a ≠ b, γ = 90˚
– Square a = b, γ = 90˚
– Hexagonal a = b, γ = 120˚
• Square and hexagonal lattices can’t be
centered

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 Plane Lattices

Also called a
rhombic lattice.

• What happens if you

try to center square or
hexagonal lattices?

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Unit Cells NOT!

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 Rotation Operations

C 2, 2 No other rotations are

compatible with translational
symmetry.
C 3, 3

C 4, 4

C 6, 6

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Glide Planes

b-glide plane illustrated

perpendicular the plane “of
the paper”. The square of the
operation is a unit translation
along b.

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 Plane Groups
Rectangular
Oblique Square Hexagonal
primitive centered

p1 pm cm p4 p3

p2 pmm cmm p4m p6

pg p4g p31m

pgg p3m1

pmg p6m

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Plane Groups (Full Symbols)
Rectangular
Oblique Square Hexagonal
primitive centered

p1 p1m1 c1m1 p4 p3

p211 p2mm c2mm p4mm p6

p1g1 p4gm p31m

p2gg p3m1

p2mg p6mm

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 Notation for Full Symbols
1) 1st symbol, p or c: primitive or a face-centered.
2) 2nd symbol, n: highest rotational symmetry: 1-fold
(none), 2-fold, 3-fold, 4-fold, or 6-fold.
3) 3rd symbol, m, g, or 1, for mirror, glide reflection,
or none: These indicate symmetries relative to one
translation axis of the pattern, referred to as the
"main" one. If there is a mirror perpendicular to a
translation axis we choose that axis as the main
one (or if there are two, one of them). The axis of
the mirror or glide reflection is perpendicular to the
main axis for the first letter, and either parallel or
tilted 180˚/n (when n > 2) for the second letter.

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 Symmetry not shown in
Notation & Short Symbols
4) Many groups include other symmetries implied
by the given ones. The short notation drops
digits or an m that can be deduced, so long as
that leaves no confusion with another group.

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Plane Groups

(see Cotton, Chapter 10)

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Plane Groups

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Building up Groups from Generators
The philosophy of the Hermann-Mauguin
(international) notation is to supply the
minimal number of group operations in
the group symbol (and those operations
generate the rest…).
• Point group examples:
C2v = mm ; D2h = mmm ; C4v = 4mm ;
4/m mm = ? ; 422 = ? ; 42m = ? ; 3m = ?

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 Plane and Space Groups add
translations as additional Generators
In plane (and space) groups, the symbols
convey information about the whether
the lattice is primitive or centered plus
point group operation information.
Translations and operations that are
products of point group operations with
each other or with translations are
assumed to be generated.
• Examples:
p1 ; pm ; p2 ; pg ; pmm ; p4m

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 p1

p1
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 pm

pm
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 p2

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Oblique lattices can’t have mirrors

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 pg

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pmm

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p4m
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Plane Group symmetries from Symbol: pgg

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 Identifying plane groups: Examples

Unit Cell?

Symmetry Operations?

p4g

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Identifying plane groups: Examples

Unit Cell?

Symmetry Operations?

cmm

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 Identifying plane groups: Examples

Unit Cell?

Symmetry Operations?

p4g

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Identifying plane groups: Examples

Unit Cell?

Symmetry Operations?

pgg
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Identifying plane groups: [NiF4]2– (flattened)

Symmetry Operations?

Unit Cell?

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Identifying plane groups: PtS2 (flattened)

Symmetry Operations?

Unit Cell?

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Identifying plane groups: CaB2C2 (B-C nets)

Unit Cell?

Symmetry Operations?

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Identifying plane groups: one graphite layer

Symmetry Operations?

Unit Cell?

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Plane Group Flowchart

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Identifying plane groups: Examples

Unit Cell?

Symmetry Operations?
(not) ignoring colors

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Identifying plane groups: Examples

Unit Cell?

Symmetry Operations?
(not) ignoring colors

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 p3m1 vs. p31m
p3m1
p31m

p3m1 has mirror planes through all the 3-fold

axes, p31m has mirror planes through one
kind of the 3-fold axes.
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Identifying plane groups: Examples

Unit Cell?

Symmetry Operations?
(not) ignoring colors

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 Group Theory: Comments
• Space groups are groups: they have all the
properties you learned about point groups, but
are of infinite order.
• We won’t worry about the irreducible
representations of space groups in this class,
but the group theoretic machinery when applied
to crystals is very powerful! Just as for point
groups, the more symmetry that is present, the
more symmetry can be used to simplify physical
problems.
• Lattices are associated with the infinite-order
translational subgroup of space groups.

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 (Non)symmorphic Groups
• Symmorphic space groups are direct product groups of
one of the 32 crystallographic point groups and the
translation group (i.e., every operation is a product of a
translation and a simple point group operation).
• Nonsymmorphic space groups contain elements (glide
planes and or screw axes) that are not simply generated
as a product of a lattice translation with a point group
operation.
• Symmorphic space (and plane) groups normally do not
have screw axis or glide plane symbols appear in their
symbols (though this rule can be relaxed when the setting
chosen for the unit-cell axes is changed).
• A symmorphic space group must have at least one point
in the cell with a site symmetry which is the same as the
point group of the space group.
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 Bravais Lattices
• Direct Lattice:
– A regular, periodic array of points with a spacing
commensurate with the unit cell dimensions. The
environment around all points in a lattice is identical.
• The set of direct lattice points can be written as
(vectors):
R = ta + ub + vc

t, u, v : integers
• V = volume of unit cell

V = a ⋅ (b × c ) = b ⋅ (c × a ) = c ⋅ (a × b)

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 3-D Lattices
• 14 Bravais Lattices - fall under 7 crystal systems
• Triclinic a ≠ b ≠ c, α ≠ β ≠ γ

• Monoclinic a ≠ b ≠ c, α = γ = 90°, β − no condition

– Primitive and body centered (I-centered)

• Orthorhombic a ≠ b ≠ c, α = β = γ = 90°
– One-faced centered (A-, B, C- centered)
– Body centered (I-centered)
– Face centered (F-centered)

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 (b-axis unique)

Bravais
Lattices

(c-axis vertical)

http://isis.ku.dk/kurser/index.aspx?
kursusid=27416&xslt=simple6&param1=205806&param8=false

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 Bravais
Lattices,
continued

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 32 Crystallographic Point Groups
Hermann-Mauguin
1, 1,2,m,2 m,mm,222,
mmm,4, 4,4 m,4mm, 42m,
422,4 m mm,3, 3,3m,32, 3m,
6,6,6 m,6m2,6mm,622,
6 m mm,23,m3, 43m,432,m3m
Schoenflies
C1 ,Ci ,C2 ,Cs ,C2h ,C2v , D2 ,
D2h ,C4 ,S4 ,C4h ,C4v , D2d ,
D4 , D4h ,C3 ,S6 ,C3v , D3 , D3d ,
C6 ,C3h ,C6h , D3h ,C6v , D6 ,
D6h ,T ,Th ,Td ,O,Oh

• These are all the point symmetries compatible

with translational symmetry of crystals.

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 Structures vs. Lattices
• What is the distinction between a structure and a
lattice?
• Consider the two-dimensional “honeycomb net” of a
graphite layer

Q: Do the carbon atom

positions constitute a
“lattice”?

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 Graphite - 3D

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Glide Planes
b-glide plane illustrated
perpendicular the plane “of the
paper”. Square of the operation
is a unit translation along b.

n-glide (diagonal glide) plane

illustrated in the plane “of the
paper”. ‘Comma’ indicates that
the object is flipped over.
perpendicular the plane “of the
paper”. Square of the operation
is a unit translation along a + b.

in tetragonal and cubic, n-glides

involving a (a + b + c)/2 trans-
lation are possible (with a
component ⊥ to the plane).

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 41 Screw Axis

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 Screw
Operations

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Screw Operations

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Space Group Operations

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Space Group Symbols & Notation

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Space Group Symbols

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 List of Space Groups with
High Resolution Diagrams

http://img.chem.ucl.ac.uk/sgp/large/sgp.htm

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PtS - example

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P4/m; All the info in the symbol

Perform
Apply 4-fold
Recognizetranslations
2-fold
rotation
axes
andand
m additional
reflection;
recognize
inversioninversion
centers

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 Two
Symmorphic,

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Triclinic Space Groups: P1 & P1

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 Orthorhombic
Space Groups

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 Orthorhombic
Space 


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β-Sn (White Tin)

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