Introduction to Infrared and Raman Spectroscopy

by Colthup; Daly; Wiberley

• ISBN13: 9780121825546
• ISBN10: 012182554X
• eBook ISBN(s): 9780121825546
• Additional ISBN(s): 9780080917405
• Edition: 3rd
• Format: Hardcover
• Copyright: 1990-08-28
• Publisher: Elsevier Science

Summary

Now in its third edition, this classic text covers many aspects of infrared and Raman spectroscopy that are critical to the chemist doing structural or compositional analysis. This work includes practical and theoretical approaches to spectral interpretation as well as a discussion of experimental techniques. Emphasis is given to group frequencies, which are studied in detailed discussions, extensive tables, and over 600 carefully chosen and interpreted spectral examples. Also featured is a unique treatment of group frequencies that stresses their mechanical origin. This qualitative approach to vibrational analysis helps to simplify spectral interpretation. Additional topics include basic instrumental components and sampling techniques, quantitative analysis, Raman polarization data, infrared gas contours, and polarized IR studies, among others.

Table of Contents

Preface	xi
Vibrational and Rotational Spectra	1	(74)
Introduction	1	(1)
Photon Energy	2	(1)
Degrees of Freedom of Molecular Motion	3	(1)
Normal Modes of Vibration	4	(1)
Mechanical Molecular Models	4	(2)
Coordinates Used to Describe Molecular Vibrations	6	(1)
Classical Vibrational Frequency Formula for Diatomic Molecular	7	(4)
Infrared Absorption and the Change in Dipole Moment	11	(4)
Anharmonicity and Overtones	15	(1)
Vibrational Potential Function	16	(3)
Introduction to the Quantum Effect	19	(4)
The Quantum Mechanical Harmonic Oscillator	23	(2)
The Boltzmann Distribution Function	25	(1)
Vibrational Transitions and Infrared Absorption	26	(1)
The Anharmonic Oscillator	27	(3)
Combination and Difference Bands	30	(1)
Fermi Resonance	31	(2)
Rotation of Linear Molecules	33	(4)
Rotational Transitions and Infrared Absorption	37	(4)
The Nonrigid Rotator	41	(1)
Rotational Line Intensities	42	(1)
Types of Rotators	43	(2)
Rotation of Symmetric Top Molecules	45	(1)
Vibrational-Rotational Spectrum, Classical Picture	46	(2)
Vibrational-Rotational Spectrum, Quantum Mechanical Treatment	48	(6)
Vibrational-Rotational Spectrum, Nonrigid Rotator	54	(2)
Spherical Top Molecules	56	(1)
Symmetrical Top Molecules	56	(2)
Asymmetrical Top Molecules	58	(2)
The Raman Effect	60	(2)
Polarizability	62	(3)
The Tensor Character of the Polarizability	65	(3)
Depolarization Ratio	68	(2)
Pure Rotational Raman Spectra	70	(2)
Raman Sources	72	(3)
IR Experimental Considerations	75	(34)
Source of Infrared Radiation	75	(2)
Infrared Detectors	77	(1)
Monochromators	77	(3)
Interferometers	80	(3)
Infrared Transmiting Materials	83	(1)
Salt Polishing	84	(1)
Infrared Cells	85	(2)
Solid Sampling	87	(5)
Internal Reflection Spectroscopy	92	(2)
Polarized Infrared Radiation	94	(6)
Quantitative Analysis	100	(9)
Molecular Symmetry	109	(62)
Symmetry Properties	109	(6)
Point Groups	115	(4)
Group Theory	119	(2)
Group Theory Applied to Point Groups	121	(3)
Representations of Groups	124	(5)
Irreducible Representations	129	(2)
The Character Table	131	(5)
Irreducible Representation Components in a Representation	136	(2)
Transformation Properties of a Vector	138	(1)
The Number of Fundamentals of Each Type	139	(2)
Selection Rules	141	(3)
Infrared Activity of Fundamentals	144	(1)
Raman Activity of Fundamentals	145	(1)
Overtone and Combination Bands	146	(4)
Symmetry Coordinates	150	(2)
Isotope Effects and the Product Rule	152	(3)
Character Tables and Selection Rules	155	(16)
The Vibrational Origin of Group Frequencies	171	(44)
Introduction	171	(1)
Diatomic Oscillators	172	(1)
Coupled Oscillators	172	(3)
Unsymmetrical Coupled Oscillators	175	(2)
X---H Stretching Frequencies	177	(1)
Triple Bond Vibrations	178	(2)
Cumulated Double Bonds	180	(1)
The Linear M1---M2---M3 Model	181	(1)
X---C≡N Compounds	182	(2)
Carbony1 and C=C Compounds	184	(4)
Cyclic Compound Stretching Vibrations	188	(4)
The Bent M1---M2---M1 Stretching Frequencies	192	(2)
Noncyclic Single Bond Vibrations	194	(2)
Bend-Bend Interaction	196	(6)
Bend-Stretch Interaction	202	(5)
Multiple Oscillator Groups	207	(1)
Interaction Force Constant Effects	208	(2)
Hydrogen Bonding	210	(5)
Methyl and Methylene Groups	215	(20)
Introduction to Group Frequencies	215	(1)
Methy1 Groups	216	(1)
CH3 Stretching Vibrations	217	(5)
CH3 Deformation Vibrations	222	(3)
CH3 Rock Vibrations	225	(2)
Methylene Groups	227	(1)
CH2 Stretching Vibrations	228	(1)
CH2 Deformation Vibrations	228	(1)
CH2 Wag Vibrations	228	(2)
CH2 Rock Vibrations	230	(2)
CH2 Twisting Vibrations	232	(1)
CH2 in Cyclic Compounds	232	(1)
Carbon Hydrogen Group	233	(2)
Triple Bonds and Cumulated Double Bonds	235	(12)
Introduction	235	(1)
Monosubstituted Acetylenes	236	(1)
Disubstituted Acetylenes	237	(1)
Allenes	238	(1)
Nitriles	238	(1)
Nitrile N-Oxides and Complexes	239	(1)
Cyanates	239	(1)
Isocyanates	239	(1)
Thiocyanates	240	(1)
Isothiocyanates	240	(1)
Nitriles on a Nitrogen Atom	240	(1)
Carbodiimides	241	(1)
Ketene Imines	241	(1)
Diazo Compounds	241	(2)
Azides	243	(1)
Aryl Diazonium Salts	243	(1)
Isocyanides	244	(1)
Ketenes	244	(1)
Cyanide Ions	244	(1)
Cyanate Ions	245	(1)
Thiocyanate Ions	245	(1)
Metal Carbonyls	245	(1)
Three and Four Cumulated Double Bonds	245	(2)
Olefin Groups	247	(14)
Noncyclic Olefins	247	(5)
Olefinic Hydrogen Wagging Vibrations	252	(5)
Cyclic C=C	257	(4)
Aromatic and Heteroaromatic Rings	261	(28)
Benzene Rings	261	(2)
The Carbon-Carbon Vibrations	263	(1)
The 1600 cm-1 Region	264	(2)
The 1500 cm-1 Region	266	(1)
The 700 cm-1 Region	267	(1)
The 900-700 cm-1 CH Wag Bands	268	(7)
The 2000-1650 cm-1 Summation Bands	275	(1)
The 1300-1000 cm-1 Region	276	(3)
The 850-600 cm-1 Region	279	(1)
The 550-400 cm-1 Region	280	(1)
Condensed Ring Aromatic Compounds	281	(2)
Pyridines	283	(1)
Pyridine N-Oxides	283	(1)
Pyrimidines	284	(1)
Triazines	284	(1)
Alkyl- or Aryl-Substituted Triazines	284	(1)
Melamines and Guanamines	285	(1)
Chloro-, Oxy-, and Thio-Substituted Triazines	285	(1)
Tetrazines	286	(1)
Heteroaromatic Five-Membered Ring Compounds	286	(2)
Cyclopentadienyl Ring-Metal Complexes	288	(1)
Carbonyl Compounds	289	(38)
Introduction	289	(1)
Mass Effects	289	(3)
Bond Angle Effects	292	(1)
Inductive Effects	293	(1)
Mesomeric Effects	294	(1)
Ketones	295	(1)
α-Chloro Ketones	295	(1)
Conjugated Ketones	296	(1)
Conjugated Hydrogen Bonded Ketones	297	(2)
Bond Angle Effects in Ketones	299	(1)
Aldehyde CH Vibrations	300	(1)
Aldehyde Carbonyl Vibrations	301	(1)
Aldehyde C---C	301	(1)
Ester C=O	301	(1)
Ester C---O	302	(3)
Out-of-Plane Hydrogen Vibrations in Unsaturated Esters	305	(1)
Groups Next to the Carbonyl in Esters	306	(1)
Groups on the Oxygen Atoms in Esters	307	(1)
Lactones	307	(1)
Thiol Esters and Related Compounds	308	(1)
Organic Carbonate Derivatives and Related Compounds	309	(1)
Oxalates	310	(1)
Anhydrides	310	(2)
Peroxides, Acyl or Aroyl	312	(1)
Halogen-Substituted Carbonyls	312	(1)
Carboxylic Acid OH Stretch	313	(1)
Carboxyl-Carbonyl Stretch	313	(2)
Carboxyl OH Bending and C---O Stretching	315	(1)
Monomeric Acids	315	(1)
Aliphatic Peroxy Acids	316	(1)
Aromatic Acids	316	(1)
Aliphatic Bands in Long Chain n-Aliphatic Carboxylic Acids, Ester, and Soaps	317	(1)
Carboxyl Salts	317	(1)
Amino Acids	318	(1)
Amido Acids	319	(1)
Unsubstituted Amides	319	(1)
N-Substituted Amides (trans)	320	(1)
N-Substituted Amides (cis) (Lactams)	321	(1)
Disubstituted Amides	322	(1)
Ureas	322	(1)
Carbamates	323	(1)
Hydroxamic Acids	323	(1)
Imides	323	(1)
Isocyanurates	324	(1)
Acid Hydrazides	325	(2)
Ethers, Alcohols, and Phenols	327	(12)
Aliphatic Ethers	327	(1)
Aromatic Ethers	328	(1)
Vinyl Ethers	329	(2)
Cyclic Ether Linkages	331	(1)
Oxirane Ring Compounds	331	(1)
OH Stretch in Alcohols and Phenols	332	(1)
C---O Stretch	333	(1)
OH Deformation	334	(1)
Phenols	334	(1)
Noncyclic Acetals and Related Compounds	335	(1)
Cyclic Acetals	335	(1)
Carbohydrates	335	(1)
Peroxides	336	(3)
Amines, C=N, and N=O Compounds	339	(16)
NH2 Stretch in Amines	339	(1)
NH2 Deformation in Amines	340	(1)
NH	340	(1)
C---N in Aliphatic Amines	341	(1)
C---N in Aromatic Amines	341	(1)
Aliphatic Bands in Amines	342	(1)
The Ammonium Ion	343	(1)
Amine Salts	343	(1)
C=N Groups	344	(2)
Nitro Group	346	(3)
Organic Nitrates	349	(1)
Nitramines	349	(1)
Organic Nitrates	350	(1)
Inorganic Nitrates and Nitrites	350	(1)
N=N Azo	350	(2)
Azoxy and Azothio Groups	352	(1)
C-Nitroso Compounds	353	(1)
Nitrosamines	354	(1)
Compounds Containing Boron, Silicon, Phosphorus, Sulfur, or Halogen	355	(32)
Boron Compounds	355	(1)
B---O	355	(1)
B---OH	356	(1)
B---N	356	(1)
B---H	357	(1)
B---Cl	357	(1)
B---CH3	358	(1)
B---Phenyl	358	(1)
Silicon Compounds	358	(1)
Si---H	359	(1)
Si---CH3	360	(1)
Si---CH2---R	360	(1)
Si---C6H5	360	(1)
Si---CH=CH2	360	(1)
Si---O---R	361	(1)
Si---O---C6H5	361	(1)
Si---O---Si	361	(1)
Si---OH	361	(1)
Si---Halogen	362	(1)
Si---N	362	(1)
Phosphorus Compounds	362	(1)
P---H	363	(1)
P---O	364	(1)
P---OH	365	(1)
P---O---P	365	(1)
PO2-, POS-, PO32-, PO43-	366	(1)
P---O---C (Aliphatic)	366	(1)
P---O---C (Phenyl)	367	(1)
P---CH2	367	(1)
P---CH3	367	(1)
P---Phenyl	367	(1)
P=S	368	(2)
P=SH	370	(1)
P---N	370	(1)
P=N	370	(1)
P---F, P---Cl, P---C	371	(1)
S---H	371	(1)
Sulfides and Disulfides	371	(1)
CH2---S	372	(1)
CH3---S	372	(1)
S---CH=CH2	372	(1)
S---Aryl	373
S---F	273	(100)
SO	373	(1)
SO2	373	(1)
Sulfones	374	(1)
Sulfonamides	375	(1)
Sulfonic Acids	375	(1)
Sulfonic Acid Salts	375	(1)
Sulfinic Acids	375	(1)
HSO4-	376	(1)
SO42-	376	(1)
SO32-	376	(1)
S---O---CH2	376	(1)
Thionylamine	376	(1)
C=S	377	(2)
(FHF)-	379	(1)
FCH	379	(1)
FC=C	380	(1)
FC=O	380	(1)
F---Aryl	380	(1)
CF Stretch	380	(1)
C---Cl	381	(2)
C---Br	383	(2)
C---I	385
Aryl Halides	383	(1)
Organometallic Compounds	384	(1)
Inorganic Metal Oxides	385	(2)
Major Spectra-Structure Correlations by Spectral Regions	387	(96)
Introduction	387	(1)
3700-3100 cm-1 (OH, NH, and =CH)	387	(1)
3100-2980 cm-1 (Aryl, Olefinic, and Three-Membered Ring CH)	388	(1)
3000-2700 cm-1 (Aliphatic CH)	388	(1)
3100-2400 cm-1 (Acidic and Strongly Bonded Hydrogens)	389	(1)
2600-2100 cm-1 (SH, BH, PH, and SiH)	389	(1)
2300-1900 cm-1 (X=Y and X=Y=Z)	389	(1)
2000-1700 cm-1 (Aryl and Olefinic Overtones)	389	(1)
1900-1550 cm-1 (C=O)	390	(1)
1700-1550 cm-1 (C=C and C=N)	390	(1)
1600-1450 cm-1 (N=O)	390	(1)
1660-1500 cm-1 (NH2, NH3+, and CNH)	391	(1)
1620-1420 cm-1 (Aromatic and Heteroaromatic Rings)	391	(1)
1500-1250 cm-1 (CH3 and CH2)	391	(1)
1470-1310 cm-1 (B---O,B---N,NO3-,CO32-, and NH4-	391	(1)
1400-1000 cm-1 (SO2, SO3-, SO, and SO42-)	392	(1)
1350-1120 cm-1 (CF, and CF2	392	(1)
1350-1150 cm-1 (CH2 and CH wag)	392	(1)
1300-1000 cm-1 (C--O)	392	(1)
1100-830 cm-1 (Si-O and P-O)	393	(1)
1000-600 cm-1 (Olefinic and Acetylenic CH-wag)	393	(1)
900-700 cm-1 (Aromatic CH Wag)	393	(1)
830-500 cm-1 (CCI, Cbr, and CI)	393	(1)
900-500 cm-1 (OH, NH, and NH2 Wag)	393	(1)
800-200 cm-1 (Selected Inorganic Absorptions)	394	(1)
Mixtures	394	(1)
Correlation charts	395	(3)
Selected Infrared Spectra Illustrating Functional Group Frequencies	398	(80)
Selected Raman Spectra	478	(5)
The Theoretical Analysis of Molecular Vibrations	483	(60)
Normal Modes of Vibration	483	(3)
The Linear Triatomic Model's Stretching Frequencies	486	(4)
Internal Coordinates	490	(1)
Vibrational Solution Using Internal Coordinates	491	(2)
The G Matrix	493	(4)
The L Matrix	497	(1)
Normal Coordinates	498	(2)
Potential Energy Distribution	500	(1)
The Form of the Normal Coordinates	501	(1)
Symmetry Coordinates	502	(3)
The CHCI3 Molecule	505	(3)
The Internal Coordinates for CHCI3	508	(1)
The Symmetry Coordinates for CHCI3	509	(9)
The G Matrix for CHCI3	518	(8)
The F Matrix for CHCI3	526	(2)
The Secular Determinants for CHCI3	528	(1)
The Frequencies of the CDCI3 Molecules	529	(1)
Comparison of Experimental and Calculated Wavenumbers	530	(1)
The Form of the Chloroform Normal Coordinates	530	(5)
The Potential Function Problem	535	(1)
A Review of Matrix Notation	536	(3)
The Normal Coordinate Problem in Matrix Form	539	(4)
Index	543