Table Of ContentPROGRESS
IN
INFRARED
SPECTROSCOPY
Volume 1
PROGRESS
IN
INFRARED
SPECTROSCOPY
Volume 1
edited by
Herman A. Szymanski
Proceedings of the
Fifth Annual Infrared Spectroscopy Institute
Held at Canisius College, Buffalo, New York
August 14-18, 1961 ·
Springer Science+Business Media, LLC
1962
Library of Congress Catalog Card Number 62-13472
ISBN 978-1-4899-6963-7 ISBN 978-1-4899-7009-1 (eBook)
DOI 10.1007/978-1-4899-7009-1
©1962 Springer Science+Business Media New York
Originally published by Plenum Press, Inc. in 1962
Softcover reprint of the hardcover 1st edition 1962
Additional material to this book can be downloaded from http://extras.springer.com.
All rights reserved
No part of this publication may be reproduced in any
form without written permission from the publisher
Contents
lntroduction to Theoretical Infrared Spectroscopy
by Herman A. Szymanski I
How Group Frequencies Are Assigned
by Herman A. Szymanski and Lowell Karre 7
Infrared Spectra Correlation of Plastics and Resins
by A bram Davis 17
lntroduction to lnorganic Infrared Spectroscopy
by lohn R. Ferraro 35
Interpretation of the Infrared Spectra of lnorganic Molecules
by lohn R. Ferraro 53
Infrared Instrumentation - Past, Present, and Future:
A General Survey
by Martin H. Gurley, lll 63
High-Resolution Instrumentation: Advantages
and Applications
by Charles D. Kennedy 73
A New Double-Beam Far-Infrared Spectrophotometer
by R. E. Anacreon, C. C. Helms, and E. H. Siegler 87
Far-Infrared Spectrometry
by F. F. Bentley 99
Applications of the Far-Infrared Region Beyond 35 Microns
by lohn R. Ferraro ll5
Some Studies with Far-Infrared Spectroscopy
by Herman A. Szymanski 121
Absolute lntensities of Vibrational Absorption Bands
by William 1. Driscoll 125
Sampling for Spectrophotometry with Special Reference to
the Use of the Potassium Bromide Disk Technique
by Sister Miriam Michael Stimson, O.P. 143
Infrared Quantitative Analysis: General Comments on
Instrumental Conditions ·for Quantitative Analysis
by Lewis E. Tufts and Abram Davis 151
Iudustrial Quantitative Infrared Analysis
by A. S. Ayers 167
Applications of Raman Spectroscopy
by lohn R. Ferraro 173
Raman Spectroscopy at Canisius College
by Herman A. Szymanski 183
Group Theory
by ]oseph Ziomek 187
Analytical Applications of Ultraviolet, Visible, and
Near-lnfrared Absorption ~pectrophotometry
by Robert G. White 237
Integration of Nuclear 1\lagnetic Resonance Spectroscopy
with an Infrared Spectroscopy Laboratory
by Herman A. Szymanski 355
Bibliography of Infrared Spectrophotometry and
Raman Spectra
by Austin V. Signeur 379
Appendix 435
Introducdon to Theoretical
Infrared Spectroscopy
Herman A. Szymanski
Canisius College
Buffalo, New Y ork
I would like to present some ideas on band contours and types
of vibrations that I think may be of help to the spectroscopist un-
familiar with some of the more theoretical aspects of infrared spec-
troscopy. In addition, I would like to compare the concept of "group
frequencies" to a concept of infrared theory termed "correlation
tables." These correlation tables, I think, can be as useful in some
infrared analyses as the concept of "group frequencies." To present
these ideas in a short time, I shall specifically discuss only one series
of compounds, namely, the series CHa-CFa, CHa-CF2Cl,
CHa-CFCb, and CHa-CCb. First, Iet me introduce the concept of
a "species" of vibration, limiting the discussion specifically to the
species of vibrations of CHa-CFa and CHa-CCb.
These two molecules have three species of vibrations, classified
as A 1. A2, and E. I shall explain each of these in terms of the motion
the atoms of each molecule undergo during these types of vibration.
First Iet us consider the symmetry of the molecules CHa-CFa and
CHa-CCb. I shall assume that the three H and three F atoms are
spaced symmetrically around the carbon atom to which they are
attached. If an axis were visualized as passing through the two car-
bon atoms, then both these molecules, CH3-CF3 and CH3-CCia,
would have a symmetry designated as C3 •• A group such as Ca. im-
plies that there are three symmetrical rotations about the major
axis of symmetry and three reflection planes that are also along this
1
2 Herman A. Szyrnanski
major axis of symmetry. Each reflection or rotation must be such
that it only changes equivalent atoms. The three rotations for these
two molecules are then rotations of 0, 120, and 240° about the axis
passing through the two carbon atoms, The reflections can be con-
sidered to have mirror planes which include the major axis and which
pass through one H and one F (or one H and one Cl) atom and
bisect the other two H and two F atoms. Since there are three H
and three F ( or three Cl) atoms, there are three planes of reflec-
tion passing through the C-C axis and they are at angles of 120°
from each other. We need to visualize both the rotation axis and
the planes of reflection, so we can describe the species of vibra-
tions in terms of these two symmetry conditions.
Let us now consider the A1 vibrations for CHa-CFa and
CHa-CCia. An A1 vibration for CHa-CFa and CHa-CCb is de-
fined as one where the atoms move in such a manner that the mo-
tion is symmetrical with respect to both the axis of rotations and
the planes of reflection in the molecule. Since we can visualize the
axis of rotations and the planes of reflections for these two mole-
cules, it should be possible to show that what are called symmetri-
cal stretches of the structures C-C, C-F, C-H, and C-Cl are
all A1 vibrations. A symmetrical stretching frequency can be visu-
alized as one where the atoms move in and out in phase. For example,
for -CHa the three atoms could move as a unit away from and
toward the carbon atom in a vibrating motion.
There are also two symmetrical bending vibrations which are
A1 vibrations for these two molecules. These are the symmetrical
bendings of the CHa and CFa groups. This motion is one where
the bonds are bent symmetrically rather than stretch as in the
previous case. W e can visualize this bending for CHa by drawing
the hydrogens spaced equidistant from each other and from the car-
bon. The three can now bend toward and away from the axis formed
by the carbon and the center of the plane of the three hydrogens.
The second type of vibration that occurs for these two mole-
cules is classified as A2 species. By definition this vibration is one
which is symmetrical with respect to the planes of symmetry that
exist in these molecules. Only one kind of motion can be visualized
for CHa-CF2 and CHa-CCb that can be considered as being an
A2 vibration. This is a motion where a group such as CHa, CFa, or
CCb twists around the C-C axis. I t is called a torsional mode.
Such a vibration is inactive in the infrared region for these two
molecules. The student should try to visualize the motion involved
lntroduction to Theoretical Infrared Spectroscopy 3
here so he can see that it would be symmetrical with respect to the
axis of rotation of the molecule and antisymmetrical with respect to
the planes of reflectiono W e can diagram the torsional motion in
the following way o
The arrow indicates a twist around the C-C bond of the CHa
groupo
The last species of vibrations that can occur for these two mole-
cules is classified as a type Eo This type of vibration is doubly de-
generate, that is, two vibrationsexist of the exact same energyo The
E type vibration is also antisymmetrical with respect to rotational
axes that exist in the molecule. For the two molecules CHa-CFa
and CHa-CCla, the vibrations that can be called rocking of the
CCla, CHa, and CFa groups and C-H, C-F, and C-Cl stretches
are E vibrationso In addition, some of the deformations of the C-H,
C-F, and C-Cl groups are E type vibrationso
Let us now consider a correlation table formed by tracing the
vibrations ofCHa-CFa through the series CHa-CF2Cl,CHa-CFCb
to CHa-CClao Such a table is shown in Figo 1. The vibrations for
CHa-CFa are given in the first row of the table with the species
of the vibration listed for each vibrationo A solid verticalline denotes
infrared bands; a broken line indicates Raman bandso Coincident
infrared and Raman bands are denoted by slightly separated lineso
A dotted line indicates frequencies derived from overtone or com-
bination bandso The relative intensities of the bands are indicated
by the heights of the vertical lineso Correlation lines are drawn so
as to connect similar species of vibrationso Solid correlation lines
denote symmetry o Crossings of lines connecting the same pair of
species may not occuro This restriction makes it possible to follow
a similar vibration through a series of molecules and assign the vi-
bration to any member of the series if the vibration is known for
the members above and below the one to which the assignment is
to be madeo In some applications these correlation lines are more
useful than the so-called "group frequency" assignmentso For ex-
ample, in the series of compounds shown in Figo 1 only the vibra-
tions involving C-H stretching, methyl deformation, and torsion
..
0 100 200 300 400 ~00 tiOO 700 IIUO 110- - ·0-0-0- ·1-2-0-0 1- 4--00~ 1·-6-0-0 3000 CM"I
T IIOCCFI;sI ~;J Ie-e IICOHC ~ C H
·~· I
CH 1·C F;s zi [I E ~ Al 'I' r ~ J J I A :r Al~ I
I
CHjC [I Cl .I' I,
l/ I/ /~ !f l j IV II!} .,/ I~ I I I j I
I I I V . " rr /lv
ji.'H1·C Cl 2 :!II jI
I/ ~~I- / V !I ......... \~ : ~ j I I
I II f,I I 1
~ V I :.I. ......-V j//
I ,... I
CHjC Ii A I:. E ~Al iA1 !Ir ... ~~ Al~
~ ll• a.lf fjr =~
-T ACOCIiCa 1'-c:- c"1' 1 --- ----- C--·0-1 c-o ~GOlClaI \ 6 r-"-•- --cI-"~" ' 9=~
[IJ
Fig. l. The fundamental vibration frequencies of CHs-CF3, CH3-CF2Cl, CH3-CFCI., and CHs-CCis. '<"EI
(Reproduced with permission from J. Chem. Phys. 20, No. 3, p. 473, March, 1952.) =
=
E"'
