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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: Chemical Analysis: A Series of Monographs on Analytical Chemistry and Its Applications
- Sprache: Englisch
Covers the advantages of using photothermal spectroscopy over conventional absorption spectroscopy, including facilitating extremely sensitive measurements and non-destructive analysis This unique guide to the application and theory of photothermal spectroscopy has been newly revised and updated to include new methods and applications and expands on applications to chemical analysis and material science. The book covers the subject from the ground up, lists all practical considerations needed to obtain accurate results, and provides a working knowledge of the various methods in use. Photothermal Spectroscopy Methods, Second Edition includes the latest methods of solid state and materials analysis, and describes new chemical analysis procedures and apparatuses in the analytical chemistry sections. It offers a detailed look at the optics, physical principles of heat transfer, and signal analysis. Information in the temperature change and optical elements in homogeneous samples and photothermal spectroscopy in homogeneous samples has been updated with a better description of diffraction effects and calculations. Chapters on analytical measurement and data processing and analytical applications are also updated and include new information on modern applications and photothermal microscopy. Finally, the Photothermal Spectroscopy of Heterogeneous Sample chapter has been expanded to incorporate new methods for materials analysis. * New edition updates and expands on applications to chemical analysis and materials science, including new methods of solid state and materials analysis * Includes new chemical analysis procedures and apparatuses * Provides an unmatched resource that develops a consistent mathematical basis for signal description, consolidates previous theories, and provides invaluable insight into laser technology Photothermal Spectroscopy Methods, Second Edition will appeal to researchers from both academia and industry (graduate students, postdocs, research scientists, and professors) in the general field of analytical chemistry, optics, and materials science, and researchers and engineers at scientific instrument developers in fields related to photonics and spectroscopy.
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Seitenzahl: 1143
Veröffentlichungsjahr: 2019
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Table of Contents
Cover
About the Authors
Preface
Acknowledgments
1 Introduction
1.1 Photothermal Spectroscopy
1.2 Basic Processes in Photothermal Spectroscopy
1.3 Photothermal Spectroscopy Methods
1.4 Application of Photothermal Spectroscopy
1.5 Illustrative History and Classification of Photothermal Spectroscopy Methods
1.6 Some Important Features of Photothermal Spectroscopy
References
2 Absorption, Energy Transfer, and Excited State Relaxation
2.1 Factors Affecting Optical Absorption
2.2 Optical Excitation
2.3 Excited State Relaxation
2.4 Relaxation Kinetics
2.5 Nonlinear Absorption
2.6 Absorbed Energy
References
3 Hydrodynamic Relaxation: Heat Transfer and Acoustics
3.1 Local Equilibrium
3.2 Thermodynamic and Optical Parameters in Photothermal Spectroscopy
3.3 Conservation Equations
3.4 Hydrodynamic Equations
3.5 Hydrodynamic Response to Photothermal Excitation
3.6 Density Response to Impulse Excitation
3.7 Solutions Including Mass Diffusion
3.8 Effect of Hydrodynamic Relaxation on Temperature
3.9 Thermodynamic Fluctuation
3.10 Noise Equivalent Density Fluctuation
3.11 Summary
Appendix 3.A Thermodynamic Parameter Calculation
Appendix 3.B Propagating Mode Impulse Response for Polar Coordinates in Infinite Media
References
4 Temperature Change, Thermoelastic Deformation, and Optical Elements in Homogeneous Samples
4.1 Temperature Change from Gaussian Excitation Sources
4.2 Thermodynamic Parameters
4.3 Thermoelastic Displacement
4.4 Optical Elements
4.5 Temperature‐dependent Refractive Index Change
4.6 Temperature Change and Thermoelastic Displacement from Top‐hat Excitation Sources
4.7 Limitations
References
5 Photothermal Spectroscopy in Homogeneous Samples
5.1 Photothermal Interferometry
5.2 Photothermal Deflection
5.3 Thermal Lens Focal Length
5.4 Detecting the Thermal Lens
5.5 Types of Photothermal Lens Apparatuses
5.6 Two‐laser Photothermal Lens Spectroscopy
5.7 Differential Two‐laser Apparatuses
5.8 Diffraction Effects
References
6 Analytical Measurement and Data Processing Considerations
6.1 Sensitivity of Photothermal Spectroscopy
6.2 Optical Instrumentation for Analysis
6.3 Processing Photothermal Signals
6.4 Photothermal Data Processing
6.5 Considerations for Trace Analysis
6.6 Tracking Down and Reducing Noise
References
7 Analytical Applications
7.1 Areas of Analytical Application
7.2 Applications to Stationary Homogeneous Samples
7.3 Application to Disperse Solutions
7.4 Photothermal Spectroscopy Detection in Chromatography and Flow Analysis
7.5 Photothermal Spectroscopy Detection in Capillary Electrophoresis
7.6 Photothermal Spectroscopy Detection in Microanalytical and Microfluidic Systems
7.7 Determination of Parameters of Reactions
7.8 Excitation and Relaxation Kinetics
References
8 Photothermal Spectroscopy of Heterogeneous Samples
8.1 Types of Heterogeneity
8.2 Apparatuses for Photothermal Deflection
8.3 Surface Absorption
8.4 Thermal Diffusion in Volume Absorbing Samples
8.5 Temperature Change in Layered Samples
8.6 Surface Point Source
8.7 Gaussian Beam Excitation of Surfaces
8.8 Gaussian Beam Excitation of Transparent Materials
8.9 Excitation of Layered Samples with Gaussian Beams
8.10 Deflection Angles with Oscillating Gaussian Excitation
8.11 Photothermal Reflection
8.12 Experiment Design for Photothermal Deflection
8.13 Application to Determination of Solid Material Properties
8.14 Applications to Chemical Analysis
References
Index
End User License Agreement
List of Tables
Chapter 1
Table 1.1 Common detection techniques used in photothermal spectroscopy.
Table 1.2 Main sample excitation schemes used in photothermal spectroscopy.
Table 1.3 Major developments in the history of photothermal spectroscopy.
Table 1.4 Absorption coefficient detection limits using photothermal and phot...
Chapter 2
Table 2.1 Relaxation times for typical gas phase species at standard temperat...
Table 2.2 Quantum yields for fluorescence and intersystem crossing.
Table 2.3 Intersystem crossing rate constants.
Table 2.4 Lifetimes of singlet oxygen in various solvents.
Chapter 3
Table 3.1 Physical properties that change by the photothermal effect.
Table 3.3 Bulk parameters used in hydrodynamic equations
Table 3.4 Approximate hydrodynamic parameters for selected substances near 25...
Table 3.5 Point source solutions for one‐, two‐, and three‐dimensional therma...
Table 3.6 Theoretical pulsed laser photothermal spectroscopy absorption coeff...
Table 3.7 Thermodynamic and optical data for common solvents and gases at 25 ...
Chapter 4
Table 4.1 Thermo‐optical constants for gases.
Table 4.3 Thermo‐optical constants for common solids.
Table 4.4 Convection limits for common solvents and gases 25 °C.
Chapter 6
Table 6.1 Photothermal properties of common gases.
Table 6.2 Photothermal properties of some liquids.
Chapter 7
Table 7.1 Applications of photothermal spectroscopy to gas phase analysis.
Table 7.2 Applications of photothermal spectroscopy to liquid phase chemical ...
Table 7.3 Applications of photothermal spectroscopy to
in vitro
/
in vivo
asses...
Table 7.4 Gas chromatography studies.
Table 7.5 Liquid chromatography studies.
Table 7.6 Flow injection analysis studies.
Table 7.7 Capillary electrophoreses and micellar electrokinetic chromatograph...
Table 7.8 Microanalytical and microfluidic studies.
Table 7.9 Gas phase energy transfer studies.
Table 7.10 Solution phase quantum yield and relaxation kinetics studies.
List of Illustrations
Chapter 1
Figure 1.1 Processes involved in photothermal spectroscopy. Absorption of rad...
Figure 1.2 Several of the mechanisms for excited state relaxation are illustr...
Figure 1.3 A generic photothermal spectrometer showing essential features.
Figure 1.4 Four methods used for photothermal spectroscopy. Interferometry di...
Figure 1.5 A simple photothermal deflection apparatus for measuring absorbanc...
Figure 1.6 Schematic of a photoacoustic spectrometer based on direct acoustic...
Figure 1.7 Schematic of an indirect photoacoustic spectrometer based on chopp...
Figure 1.8 First photothermal lens apparatus. The sample was placed in the ca...
Figure 1.9 Transient signals observed using the intracavity photothermal lens...
Figure 1.10 A schematic of the extracavity photothermal lens spectrometer use...
Figure 1.11 Illustration of the beam geometry and definitions used for extrac...
Figure 1.12 Schematic diagram of the
z
‐scan mode mismatched thermal lens appa...
Figure 1.13 Modified Jamin interferometer apparatus used by Stone (1973). Inc...
Figure 1.14 Data obtained for chlorobenzene using the photothermal interferom...
Figure 1.15 Interferometer used by Longaker and Litvak (1969) to obtain image...
Figure 1.16 Image data obtained with the apparatus illustrated in Figure 1.15...
Figure 1.17 Block diagram of photothermal polarization interferometer (see te...
Figure 1.18 The scheme of the experimental setup. HeNe laser model LGN‐302; C...
Figure 1.19 A dual‐beam photothermal lens spectrometer. The dye laser excites...
Figure 1.20 (a, b) Schematic diagram of compact thermal lens microscopes for ...
Figure 1.21 Various excitation and probe beam geometries used in photothermal...
Figure 1.22 Photothermal deflection apparatus used to measure the phototherma...
Figure 1.23 A photothermal deflection image of an aluminum surface.
Figure 1.24 One‐dimensional imaging apparatus developed for plate chromatogra...
Figure 1.25 A schematic of an apparatus used for photothermal diffraction. Th...
Figure 1.26 Schematic illustration of the setup used for photothermal cantile...
Figure 1.27 TIR‐PTDS setup with signal acquisition chain (black arrows) and c...
Figure 1.28 Experimental configuration for (a) beam deflection, (b) interfero...
Figure 1.29 The scheme of the probe used in scanning thermal microscopy (a) a...
Figure 1.30 The scheme of the experimental setup in the photothermal FTIR mic...
Figure 1.31 Schematics of photothermal FTIR microspectroscopy implemented in ...
Figure 1.32 Schematics of the experimental setup in the method of thermal emi...
Chapter 2
Figure 2.1 Optical loss processes in a transmitting sample. Incident excitati...
Figure 2.2 Three type of spectroscopy apparatuses. Transmission directly meas...
Figure 2.3 Energy‐level diagram for an organic dye molecule illustrating seve...
Figure 2.4 Energy‐level diagram illustrating the relaxation processes for rov...
Figure 2.5 Nonlinear irradiance‐dependent effects on absorbed energy. In opti...
Figure 2.6 Three‐level energy diagram used to describe kinetic effects of opt...
Figure 2.7 Three‐level energy diagram used for a kinetic description of many ...
Figure 2.8 Including excited state absorption and stimulated emission a kinet...
Figure 2.9 Effects of optical saturation on the Gaussian profile. (a) Shows t...
Chapter 3
Figure 3.1 The density change for one‐dimensional hydrodynamic relaxation of ...
Figure 3.2 Density change for one‐dimensional hydrodynamic relaxation for tim...
Figure 3.3 Propagating or acoustic mode contribution to the on‐axis density c...
Figure 3.4 Combined diffusion and propagating mode density changes for the on...
Figure 3.5 Combined diffusion and propagating mode radially dependent density...
Figure 3.6 Radially dependent density changes for Gaussian impulse excitation...
Figure 3.7 Time‐dependent density changes for Gaussian impulse excitation in ...
Figure 3.8 Time‐dependent temperature changes for Gaussian impulse excitation...
Chapter 4
Figure 4.1 Temperature change profiles produced during continuous Gaussian la...
Figure 4.2 Temperature change profiles at various times after continuous Gaus...
Figure 4.3 On‐axis heating and cooling for laser sample excitation. Part (a) ...
Figure 4.4 On‐axis heating for chopped excitation. The duty cycle is 50% with...
Figure 4.5 Relative temperature change attenuation throughout the thicknesses...
Figure 4.6 Interference pattern generated by two coherent waves adapted from ...
Figure 4.7 Temperature‐dependent thermal conductivities for water, toluene, a...
Figure 4.8 Temperature‐dependent water density.
Figure 4.9 Temperature‐dependent specific heat for water.
Figure 4.10 Relative surface displacement at various times after pulsed and c...
Figure 4.11 On‐axis relative surface displacement under pulsed and continuous...
Figure 4.12 Gaussian temperature change produced by a pulsed laser. The parab...
Figure 4.13 Relative temperature‐dependent photothermal signal for water for ...
Figure 4.14 Relative temperature change profile at various times after top‐ha...
Figure 4.15 Relative temperature change at the sample surface after a top‐hat...
Figure 4.16 Relative surface displacement profiles at various times after top...
Figure 4.17 Time‐dependent on‐axis temperature changes for a continuous laser...
Figure 4.18 Time‐dependent inverse focal length of the photothermal lens prod...
Chapter 5
Figure 5.1 Photothermal interferometry based on the Mach–Zehnder interferomet...
Figure 5.2 The trace gas detection system of Mazzoni and Davis (1991) based o...
Figure 5.3 A Fabry–Perot‐based photothermal interferometer and the resulting ...
Figure 5.4
X
‐axis deflection angle as a function of probe ray displacement in...
Figure 5.5 Time‐dependent probe ray
x
‐axis deflection signal as a function of...
Figure 5.6 Optimum probe ray offset as a function of continuous laser excitat...
Figure 5.7 Relative photothermal deflection angle as a function of the contin...
Figure 5.8 Time‐dependent photothermal deflection angle and on‐axis temperatu...
Figure 5.9 (a)–(c) Multiple cycle chopped photothermal deflection signal for ...
Figure 5.10 For long sample cells, the effective optical sample path length i...
Figure 5.11 Chopped laser‐excited inverse focal length and temperature change...
Figure 5.12 Oscillating excitation inverse focal length for collinear and cro...
Figure 5.13 Geometry used to define the theoretical photothermal lens signal....
Figure 5.14 Plot of the photothermal lens strength as a function of displacem...
Figure 5.15 Optical probe laser beam waist radius processor of Jansen and Har...
Figure 5.16 The parabolic mask used to optically process the photothermal len...
Figure 5.17 A single‐laser photothermal lens apparatus. The excitation source...
Figure 5.18 A differential photothermal lens apparatus similar to that first ...
Figure 5.19 A two‐laser photothermal lens apparatus. Separate excitation (pum...
Figure 5.20 Photothermal lens signal as a function of probe laser beam geomet...
Figure 5.21 Experimental measure of the effect of excitation laser beam waist...
Figure 5.22 Experimental measure of the relative photothermal lens signal as ...
Figure 5.23 Pulsed laser‐excited photothermal lens signal predicted from diff...
Figure 5.24 Far‐field diffraction theory predictions for pulsed laser‐excited...
Figure 5.25 Near‐field diffraction theory predictions for pulsed laser‐excite...
Figure 5.26 Continuous laser‐excited photothermal lens signal predicted from ...
Chapter 6
Figure 6.1 The calculated ratio of the sensitivity of the phase shift and pho...
Figure 6.2 The calculated ratio of the sensitivity of the phase shift and pho...
Figure 6.3 A comparison of the theoretical signal‐to‐noise ratios for transmi...
Figure 6.4 The ratio of signal‐to‐noise ratios resulting in the theoretical s...
Figure 6.5 Dependence of the sensitivity factor (as relative signal) of photo...
Figure 6.6 Experimental setup consisting of a pump source (diode pumped green...
Figure 6.7 Scheme of the white light photothermal spectrometer consisting of ...
Figure 6.8 Experimental schematic diagram of the photothermal lens apparatus ...
Figure 6.9 Sample path length dependence of the optical fiber‐based photother...
Figure 6.10 Theoretical path length‐dependent optical fiber‐based phototherma...
Figure 6.11 Scatter plots produced by measuring the excitation energy and pul...
Figure 6.12 A schematic representation of the real‐time matched filter in bot...
Figure 6.13 The calculations of relative standard deviation of measurements (...
Figure 6.14 Dependence of the relative standard deviation of thermal lens mea...
Chapter 7
Figure 7.1 Cross section of the temperature change distribution produced by c...
Figure 7.2 Time‐resolved crossed‐beam photothermal lens signal for flowing sa...
Figure 7.3 Calculated root mean square crossed‐beam photothermal lens signals...
Figure 7.4 Dependence of the thermo‐optical sensitivity coefficient
E
of phot...
Figure 7.5 Dependence of the lock‐in photothermal lens signal of Alizarin Yel...
Figure 7.6 The scheme of the experimental setup for photothermal control over...
Figure 7.7 Modified Jablonski diagram for a typical organic molecule. The dar...
Figure 7.8 Time‐resolved photothermal signal produced when there is a slow he...
Figure 7.9 The effect of optical bleaching on the pulsed laser excited photot...
Chapter 8
Figure 8.1 Photothermal deflection apparatus showing the solid sample, coupli...
Figure 8.2 Temperature changes in fluid and solid layers resulting from surfa...
Figure 8.3 Three‐layer sample.
Figure 8.4 Impulse‐response curves for the temperature change in the fluid la...
Figure 8.5 Scaled impulse response from Figure 8.4. Smaller sample absorption...
Figure 8.6 Axial relative temperature change of an opaque sample (metal) in c...
Figure 8.7 Axial relative temperature change at the interface sample (glass)–...
Figure 8.8 An illustration of the two photothermal deflection angle component...
Figure 8.9 Experimental normal and transverse optical beam deflection signal ...
Figure 8.10 A compact apparatus for photothermal deflection spectroscopy. Pro...
Figure 8.11 Two sample excitation/coupling fluid schemes. Scheme (a) requires...
Figure 8.12 Single‐beam FTIR photothermal deflection spectra of carbon black ...
Figure 8.13 Crossed‐beam photothermal lens microscope images of stained plant...
Figure 8.14 Apparatus used for crossed‐beam photothermal lens imaging microsc...
Guide
Cover
Table of Contents
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Photothermal Spectroscopy Methods
Second Edition
Stephen E. Bialkowski
Utah State UniversityLogan, UT, US
Nelson G. C. Astrath
Universidade Estadual de MaringáMaringá – PR, Brazil
Mikhail A. Proskurnin
Lomonosov Moscow State UniversityMoscow, Russia
CHEMICAL ANALYSISA Series of Monographs on Analytical Chemistry and Its Applications
Series EditorMARK F. VITHA
Editorial BoardStephen C. Jacobson, Stephen G. Weber
VOLUME 185
Vol. 1 The Analytical Chemistry of Industrial Poisons, Hazards, and Solvents
.
Second Edition
. By the late Morris B. Jacobs
Vol. 2 Chromatographic Adsorption Analysis
. By Harold H. Strain (
out of print
)
Vol. 3 Photometric Determination of Traces of Metals
.
Fourth Edition
Part I: General Aspects. By E. B. Sandell and Hiroshi Onishi
Part IIA: Individual Metals, Aluminum to Lithium. By Hiroshi Onishi
Part IIB: Individual Metals, Magnesium to Zirconium. By Hiroshi Onishi
Vol. 4 Organic Reagents Used in Gravimetric and Volumetric Analysis
. By John F. Flagg (
out of print
)
Vol. 5 Aquametry: A Treatise on Methods for the Determination of Water
.
Second Edition
(
in three parts
). By John Mitchell, Jr. and Donald Milton Smith
Vol. 6 Analysis of Insecticides and Acaricides
. By Francis A. Gunther and Roger C. Blinn (
out of print
)
Vol. 7 Chemical Analysis of Industrial Solvents
. By the late Morris B. Jacobs and Leopold Schetlan
Vol. 8 Colorimetric Determination of Nonmetals
.
Second Edition
. Edited by the late David F. Boltz and James A. Howell
Vol. 9 Analytical Chemistry of Titanium Metals and Compounds
. By Maurice Codell
Vol. 10 The Chemical Analysis of Air Pollutants
. By the late Morris B. Jacobs
Vol. 11 X‐Ray Spectrochemical Analysis
.
Second Edition
. By L. S. Birks
Vol. 12 Systematic Analysis of Surface‐Active Agents
.
Second Edition
. By Milton J. Rosen and Henry A. Goldsmith
Vol. 13 Alternating Current Polarography and Tensammetry
. By B. Breyer and H. H. Bauer
Vol. 14 Flame Photometry
. By R. Herrmann and the late C. T. J. Alkemade
Vol. 15 The Titration of Organic Compounds (
in two parts
)
. By M. R. F. Ashworth
Vol. 16 Complexation in Analytical Chemistry: A Guide for the Critical Selection of Analytical Methods Based on Complexation Reactions
. By the late Anders Ringbom
Vol. 17 Electron Probe Microanalysis
.
Second Edition
. By L. S. Birks
Vol. 18 Organic Complexing Reagents: Structure, Behavior, and Application to Inorganic Analysis
. By D. D. Perrin
Vol. 19 Thermal Analysis
.
Third Edition
. By Wesley Wm. Wendlandt
Vol. 20 Amperometric Titrations
. By John T. Stock
Vol. 21 Reflectance Spectroscopy
. By Wesley Wm. Wendlandt and Harry G. Hecht
Vol. 22 The Analytical Toxicology of Industrial Inorganic Poisons
. By the late Morris B. Jacobs
Vol. 23 The Formation and Properties of Precipitates
. By Alan G. Walton
Vol. 24 Kinetics in Analytical Chemistry
. By Harry B. Mark, Jr. and Garry A. Rechnitz
Vol. 25 Atomic Absorption Spectroscopy
.
Second Edition
. By Walter Slavin
Vol. 26 Characterization of Organometallic Compounds (
in two parts
)
. Edited by Minoru Tsutsui
Vol. 27 Rock and Mineral Analysis
.
Second Edition
. By Wesley M. Johnson and John A. Maxwell
Vol. 28 The Analytical Chemistry of Nitrogen and Its Compounds (
in two parts
)
. Edited by C. A. Streuli and Philip R. Averell
Vol. 29 The Analytical Chemistry of Sulfur and Its Compounds (
in three parts
)
. By J. H. Karchmer
Vol. 30 Ultramicro Elemental Analysis
. By Güther Toölg
Vol. 31 Photometric Organic Analysis (
in two parts
)
. By Eugene Sawicki
Vol. 32 Determination of Organic Compounds: Methods and Procedures
. By Frederick T. Weiss
Vol. 33 Masking and Demasking of Chemical Reactions
. By D. D. Perrin
Vol. 34 Neutron Activation Analysis
. By D. De Soete, R. Gijbels, and J. Hoste
Vol. 35 Laser Raman Spectroscopy
. By Marvin C. Tobin
Vol. 36 Emission Spectrochemical Analysis
. By Walter Slavin
Vol. 37 Analytical Chemistry of Phosphorus Compounds
. Edited by M. Halmann
Vol. 38 Luminescence Spectrometry in Analytical Chemistry
. By J. D. Winefordner, S. G. Schulman, and T. C. O’Haver
Vol. 39 Activation Analysis with Neutron Generators
. By Sam S. Nargolwalla and Edwin P. Przybylowicz
Vol. 40 Determination of Gaseous Elements in Metals
. Edited by Lynn L. Lewis, Laben M. Melnick, and Ben D. Holt
Vol. 41 Analysis of Silicones
. Edited by A. Lee Smith
Vol. 42 Foundations of Ultracentrifugal Analysis
. By H. Fujita
Vol. 43 Chemical Infrared Fourier Transform Spectroscopy
. By Peter R. Griffiths
Vol. 44 Microscale Manipulations in Chemistry
. By T. S. Ma and V. Horak
Vol. 45 Thermometric Titrations
. By J. Barthel
Vol. 46 Trace Analysis: Spectroscopic Methods for Elements
. Edited by J. D. Winefordner
Vol. 47 Contamination Control in Trace Element Analysis
. By Morris Zief and James W. Mitchell
Vol. 48 Analytical Applications of NMR
. By D. E. Leyden and R. H. Cox
Vol. 49 Measurement of Dissolved Oxygen
. By Michael L. Hitchman
Vol. 50 Analytical Laser Spectroscopy
. Edited by Nicolo Omenetto
Vol. 51 Trace Element Analysis of Geological Materials
. By Roger D. Reeves and Robert R. Brooks
Vol. 52 Chemical Analysis by Microwave Rotational Spectroscopy
. By Ravi Varma and Lawrence W. Hrubesh
Vol. 53 Information Theory as Applied to Chemical Analysis
. By Karl Eckschlager and Vladimir Stepanek
Vol. 54 Applied Infrared Spectroscopy: Fundamentals, Techniques, and Analytical Problem‐solving
. By A. Lee Smith
Vol. 55 Archaeological Chemistry
. By Zvi Goffer
Vol. 56 Immobilized Enzymes in Analytical and Clinical Chemistry
. By P. W. Carr and L. D. Bowers
Vol. 57 Photoacoustics and Photoacoustic Spectroscopy
. By Allan Rosencwaig
Vol. 58 Analysis of Pesticide Residues
. Edited by H. Anson Moye
Vol. 59 Affinity Chromatography
. By William H. Scouten
Vol. 60 Quality Control in Analytical Chemistry
.
Second Edition
. By G. Kateman and L. Buydens
Vol. 61 Direct Characterization of Fine Particles
. By Brian H. Kaye
Vol. 62 Flow Injection Analysis
. By J. Ruzicka and E. H. Hansen
Vol. 63 Applied Electron Spectroscopy for Chemical Analysis
. Edited by Hassan Windawi and Floyd Ho
Vol. 64 Analytical Aspects of Environmental Chemistry
. Edited by David F. S. Natusch and Philip K. Hopke
Vol. 65 The Interpretation of Analytical Chemical Data by the Use of Cluster Analysis
. By D. Luc Massart and Leonard Kaufman
Vol. 66 Solid Phase Biochemistry: Analytical and Synthetic Aspects
. Edited by William H. Scouten
Vol. 67 An Introduction to Photoelectron Spectroscopy
. By Pradip K. Ghosh
Vol. 68 Room Temperature Phosphorimetry for Chemical Analysis
. By Tuan Vo‐Dinh
Vol. 69 Potentiometry and Potentiometric Titrations
. By E. P. Serjeant
Vol. 70 Design and Application of Process Analyzer Systems
. By Paul E. Mix
Vol. 71 Analysis of Organic and Biological Surfaces
. Edited by Patrick Echlin
Vol. 72 Small Bore Liquid Chromatography Columns: Their Properties and Uses
. Edited by Raymond P. W. Scott
Vol. 73 Modern Methods of Particle Size Analysis
. Edited by Howard G. Barth
Vol. 74 Auger Electron Spectroscopy
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Second Edition
. By Stephen E. Bialkowski, Nelson G. C. Astrath, and Mikhail A. Proskurnin
This edition first published 2019© 2019 John Wiley & Sons, Inc.
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Library of Congress Cataloging‐in‐Publication Data
Names: Bialkowski, Stephen E., author. | Astrath, Nelson G. C., 1979‐ author. |Proskurnin, Mikhail A., 1967‐ author. | Bialkowski, Stephen E. Photothermal spectroscopy methods for chemical analysis.Title: Photothermal spectroscopy methods / Stephen E. Bialkowski (Utah State University, Logan, UT, US), Nelson G.C. Astrath (Universidade Estadual de Maringá, Maringá, PR, BR [Brazil]), Mikhail A. Proskurnin (Lomonosov Moscow State University, Moscow, RS).Other titles: Photothermal spectroscopy methods for chemical analysisDescription: Second edition. | Hoboken, NJ : Wiley, 2019. | Series: Chemical analysis | Previous edition: Photothermal spectroscopy methods for chemical analysis / by Stephen E. Bialkowski. | Includes bibliographical references and index. |Identifiers: LCCN 2019003717 (print) | LCCN 2019010545 (ebook) | ISBN 9781119279082 (Adobe PDF) | ISBN 9781119279099 (ePub) | ISBN 9781119279075 (hardback)Subjects: LCSH: Photothermal spectroscopy. | Spectrum analysis.Classification: LCC QD96.P54 (ebook) | LCC QD96.P54 B53 2019 (print) | DDC 543/.5–dc23LC record available at https://lccn.loc.gov/2019003717
Cover Design: WileyCover Image: Courtesy of Stephen Bialkowski
About the Authors
Nelson G. C. Astrath, PhD, is professor of physics with the Department of Physics at Universidade Estadual de Maringá (Brazil) with interests in photothermal sciences and light and matter interaction effects. He is involved in multidisciplinary international projects for CAPES, CNPq, Fundação Araucária, Fulbright, and National Research Council Canada. He has published over 100 papers in a wide array of subjects.
Stephen E. Bialkowski, PhD, is professor of chemistry with the Department of Chemistry and Biochemistry at Utah State University (United States) with interests in atmospheric chemistry, spectroscopy, nonlinear optics, and optical signal processing. He has been involved in major projects for the National Science Foundation, National Institutes of Health, Fulbright, and others; he has published over 100 papers in a wide array of subjects.
Mikhail A. Proskurnin, PhD, DSc, is professor at the Chemistry Department of M.V. Lomonosov Moscow State University. He received his PhD and DSc degrees from this university and was a visiting scientist in Tokyo University (1999–2000), FZK (Germany, 2002), and UAMS (AK, USA, 2012). He is a professor of the Russian Academy of Sciences and a member of the Scientific Council on Analytical Chemistry of the Russian Academy of Sciences. He is the author and translator of 11 books, 6 patents, and 200 papers on photothermal spectroscopy and analytical chemistry. The scientific interests lie in photonics, analytical spectroscopy, and photothermal spectroscopy in analytical and physical chemistry and applied materials science and biomedical studies.
Preface
Photothermal spectroscopy is an ultrasensitive means to measure optical and IR absorption. As such, knowledge of its operating principles should be included in the arsenal of any analytical chemist. Photothermal spectroscopy includes a variety of ingenious instrumental methods including photothermal lens, photothermal deflection, photothermal diffraction, photothermal radiometry, and photothermal interferometry spectroscopies and a host of complex experimental techniques that have not got final names yet. Some photothermal spectrometers are sensitive enough to measure absorption due to few analyte molecules: molecules that do not fluoresce. Most wishing to use photothermal spectroscopy construct their own apparatus. On the other hand, photothermal spectroscopy is a nondestructive in situ technique. It is more easily adapted to environments and applications that eluded other spectroscopies due to both its destructive nature and its finicky sample matrix requirements.
Most of the apparatuses constructed for photothermal spectroscopy analysis incorporate laser light sources. Many use lasers both for sample excitation and for monitoring changes in refractive index that occurs due to the non‐radiative energy loss of the target analyte to the supporting matrix. Signal generation is a second‐order process depending on not only the analyte but also the sample matrix and laser optics. Because of this, some argue that photothermal spectroscopy is too complicated for “practical application” to chemical analysis. This viewpoint cannot be taken after critical examination of the operating principles governing optical methods of chemical analysis in general. All processes that occur in photothermal spectroscopy also occur in conventional spectroscopies. Lasers amplify the effects of these processes through more precise control of experimental parameters. It is this magnification that allows photothermal spectroscopy to be used for ultrasensitive chemical analysis. Nonetheless, successful application of this, and any other analytical procedure utilizing laser‐based instrumentation, requires a little more caution and knowledge on the part of the analyst. Experimental observations can be controlled by processes that, in a conventional spectrometer, are simply regarded as “artifacts.” To be sure, a working knowledge of laser optics, principles governing absorption, excited state energy transfer, fluid dynamics, and measurement electronics are all necessary ingredients required to solve problems that might arise in laser‐based analysis. This knowledge constitutes a practical and consistent theoretical description of the photothermal effect.
This book on photothermal spectroscopy concentrates on the theoretical basis and practical considerations required for successful application of these techniques to the analysis of samples, primarily in homogeneous media. The final chapter discusses considerations for the analysis of solids. Photothermal spectroscopy is treated from a fundamental standpoint. Perhaps the greatest strength of this text may be that it provides a nearly complete description of photothermal spectroscopy using a common mathematical language. It is hoped that this systematic approach to a description of the physical basis for the photothermal signal generation processes will result in a more complete understanding of why certain problems are encountered in analytical applications and how the effects can either be avoided or compensated for. The information gathered to produce this description comes from many forms of analytical spectroscopy, measurement physics, physical optics, and chemical dynamics. It is information that should be known to persons doing any type of spectroscopy. As such, this book should be useful to all spectroscopists.
The book is arranged in the order of the theoretical basis and practical aspects of photothermal spectroscopy. The first chapter deals with a general description of photothermal spectroscopy and related techniques. The techniques are defined and described, and the albeit subtle distinction between photothermal and related techniques, such as photoacoustic and photopyroelectric spectroscopies, is made. The history and important features of the various techniques are given. Applications‐oriented literature is not extensively reviewed, though pertinent citations and examples are given to illustrate the points. Each part includes a discussion of the operating principles of signal generation and applications of the various techniques for materials analysis. Some parts of this chapter were based on previous review materials. Many reviews by A. C. Tam were invaluable in constructing this chapter.
Regardless of how the thermal perturbation is detected, or the physical state of the sample, the treatment of the operating principles of photothermal spectroscopy must include discussions of the optical excitation and exited state relaxation and the thermal or hydrodynamic relaxation processes. These processes are related, though, for purposes of description, they are treated in separate chapters. Optical excitation and excited state relaxation are intimately coupled to energy transfer throughout the sample matrix. Chapter 2 addresses some basic principles of optical absorption, excited state relaxation, scattering loss, and nonlinear optical absorption effects that can occur. Attention is paid to nonlinear processes, in particular those arising due to excited state dynamics. It is shown that these processes not only affect the energy absorbed by the sample but also distort the spatial distribution of absorbed energy. This spatial distortion can result in experimental artifacts in chemical analysis and so should be recognized by the analyst. These effects must be addressed for successful interpretation of nonlinear optical spectroscopies in general.
Chapter 3 addresses the hydrodynamic equations that govern energy transfer in the sample matrix. It is a necessary exercise in nonequilibrium fluid dynamics. After reviewing the literature in this area, it was decided that a new approach was needed to bring the concepts of thermal diffusion and acoustic relaxation together. The approach used is based on the solution to the energy, mass, and momentum conservation equations used by Berne and Pecora in their text describing dynamic light scattering. The approach is no more complex than others used to describe photothermal signals, but the results are more agreeable in sense that a separation of acoustic and thermal relaxation impulse responses results. The impulse‐response approach lends a more general appeal to this chapter since the results can be applied to almost any situation encountered in photothermal spectroscopy. This chapter holds some surprises. The connection between the hydrodynamic relaxation resulting from a photothermal perturbation and that resulting from statistical thermal fluctuations was not neglected. This connection allowed the calculation of detection limits based only on fundamental properties of matter. The treatment is not complete, owing to a lack of time, but it should serve as basis for a better understanding of ultimate detection limits of detection available using optical spectroscopy and to guide the analytical chemist in optimization of experimental parameters.
Chapter 4 addresses temperature change and photothermal optical element generation. It is somewhat embarrassing that much of the high‐brow theoretical aspects developed in the previous two chapters had to be discarded, or at least approximated, to provide a comprehensible description of photothermal spectroscopy. On the other hand, the approach used does accomplish certain goals. Not only is an understanding of optical element generation obtained, but also since the approximations are introduced and quantified, the limitations of this approach are recognized. Again, these may help in a description of certain artifacts that have been observed in photothermal spectroscopy. Several improvements to a quantitative description of photothermal spectroscopy are obtained in this chapter despite the approximations used. In particular, the role that excited states play in the strength of the optical elements as recognized by Terazima, and the sensitivity of the technique to temperature changes as measured and reported by Harris and Tran, may help future researchers understand and identify sources of inaccuracy when using laser‐based analysis.
A mathematical description of signals produced in photothermal spectroscopy used for homogeneous samples is shown in Chapter 5. There has been steady development in the theory since the first descriptions of the photothermal lens in the 1960s. Physical principles underlying the photothermal spectroscopy signal generation process in homogeneous samples have been addressed by many authors over subsequent years. These works are sufficiently separated in time, and approaches used are different owing to subtle differences in the area that these researchers worked in. This chapter attempts to consolidate this work by developing a consistent mathematical basis for signal description. These consolidated results are then used to make predictions to extend the understanding of photothermal spectroscopy. It is hoped that the consolidated theory can serve as a platform from which further studies into improving photothermal spectroscopy can be launched.
Chapters 6 and 7 consider successful application of photothermal spectroscopy to analytical measurements. Chapter 6 is a generalized treatment of considerations for chemical analysis. Many of the considerations are routine. In addition to the usual considerations for sampling, sample preparation, separations, reagent and solvent purity, and the like, one must also consider the thermal and optical properties of the solvents and optical materials used in the apparatus. Because of the extreme sensitivity to absorbance and the spatial‐dependent nature of the measurement, one must also be aware of how the environment affects the measurement. This chapter attempts to summarizes some of these effects and to address means by which accurate measurements can be obtained. The different means of discriminating analyte of solvent or matrix are described. The instrumental techniques for measuring the photothermal signals are then described. The instrumental apparatuses, data collection, signal processing, and data reduction steps are discussed, and virtues and limitations of the various techniques are highlighted. Chapter 7 examines the literature of analytical applications of photothermal spectroscopy.
The last chapter introduces the reader to differences between homogeneous and heterogeneous sample photothermal spectroscopy. There are now several books devoted to photothermal spectroscopy of heterogeneous materials, and this chapter only outlines the processes. This is done by examining the thermal diffusion equations that must be used to obtain a working description of the photothermal signals. A small literature review of the application of this technique to chemical analysis is included at the end.
Acknowledgments
Stephen Bialkowski would like to thank some people who, though not directly contributing to this book, did help me to complete the work. Andrew Tam brought important works in photothermal and photoacoustic spectroscopies to attention over many years through unsolicited reprints and tips. Joel Harris has been a stimulating source of personal and scientific support for endeavors into pulsed laser excited photothermal and nonlinear spectroscopies. The positive attitude of these scientists inspired me to continue writing the 1st edition in times when this book seemed hopelessly wrong. I also want to acknowledge my friend, colleague, and coauthor, Nelson Astrath. We first met the Cairo ICPPP meeting and began collaboration. Nelson inspires us to learn more about solid‐state photothermal methods, and we have made some interesting discoveries. I also acknowledge my colleague Mikhail A. Proskurnin. We also talked at the Cairo ICPPP and spoke of plans for this 2nd edition book.
Mikhail A. Proskurnin would like to cordially thank the people that worked along with me as students, but more importantly as friends and colleagues, and without whom I would be unable to do this work: Mikhail Kononets, Valerii Chernysh, Svetlana Bendrysheva, and Adelina Smirnova. Especially, I would like to say a lot of thanks to Dmitry Nedosekin, who for many years supported me in my research and never ceased to surprise me by his deep knowledge and bright ideas in photothermal sciences and who inspired many things I have reflected in this book.
I would like also to cordially thank my friends Takehiko Kitamori, Akihide Hibara, and Manabu Tokeshi with whom I worked in the wonderful world of microspectroscopy. I would like also to thank Mladen Franko and Dorota Korte for our joint studies in analytical photothermal spectroscopy for the great variety of methods and materials, which I gladly share with the readers.
I would like to express my gratitude to Vladimir Zharov who opened up the great wide open of biomedical photothermics, which changed my view of the future of photothermal spectroscopy, and several sections of this book reflect the great efforts of the community of the great people working in this field.
As well, I would like to thank my friends Andrei Luk’yanov and Ivan Pelivanov, outstanding physicists of the Russian school of physics, and their advice that helped me make more in‐depth discussion of many facets of the photothermal science.
Nelson Astrath would like to thank his mentors and friends, Mauro Baesso, Jun Shen, Luis Malacarne, and Stephen Bialkowski, each of whom has greatly influenced his commitment and passion for science. I want to thank my former students, many of whom are now friends, colleagues, and collaborators. In particular, I want to thank Gustavo Lukasievicz and Vitor Zanuto for sharing the enthusiasm.
All authors wish to acknowledge the International Conference on Photoacoustic and Photothermal Phenomena, Gordon Research Conferences, and the Fulbright and Brazilian CAPES visiting scholar programs. These all serve to bring like‐minded scientists together.
1Introduction
1.1 Photothermal Spectroscopy
Photothermal spectroscopy is a group of high sensitivity methods used to measure optical absorption and thermal characteristics of a sample. The basis of photothermal spectroscopy is a photoinduced change in the thermal state of the sample. Light energy absorbed and not lost by subsequent emission results in sample heating. This heating results in a temperature change as well as changes in thermodynamic parameters of the sample that are related to temperature. Measurements of the temperature, pressure, or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic methods.
Ingle and Crouch (1988) classify photothermal spectroscopy as one of several indirect methods for optical absorption analysis. Indirect methods do not measure the transmission of light used to excite the sample directly, but rather measure an effect that optical absorption has on the sample. The term indirect applies to the light measurement, not to the optical absorbance. Photothermal spectroscopy is, in a sense, a more direct measure of optical absorption than optical transmission‐based spectroscopies. Sample heating is a direct consequence of optical absorption, and so photothermal spectroscopy signals are directly dependent on light absorption. Scattering and reflection losses do not produce photothermal signals. Subsequently, photothermal spectroscopy more accurately measures optical absorption in scattering solutions, in solids, and at interfaces. This aspect makes it particularly attractive for application to surface and solid absorption studies and studies in scattering media.
The indirect nature of the measurement also results in photothermal spectroscopy being more sensitive than optical absorption measured by transmission methods. There are two reasons for this. First, photothermal effects can amplify the measured optical signal. This amplification is referred to as the enhancement factor (Dovichi and Harris 1979; Mori, Imashaka, and Ishibashi 1982) and is the ratio of the signal obtained using photothermal spectroscopy to that of conventional transmission spectroscopy. Enhancement factors depend on the thermal and optical properties of the sample, the power or energy of the light source used to excite the sample, and the optical geometry used to excite the sample. Since the optical excitation power or energy and geometry are variable, the enhancement can be made very large, even for samples with relatively poor thermal and optical properties. In fact, the problem with photothermal spectroscopy is not the absorption detection limit. The problem is the detection of analyte absorbance in the presence of a relatively large (10−5 cm−1) absorbance of the solvent. The second reason photothermal spectroscopy is more sensitive than transmission is that the precision of the measurement is inherently better than that of the direct transmission method. The fundamental limitation of conventional absorption spectroscopy, namely, shot noise, may be partially circumvented (Bialkowski et al. 1992). Because of the increased fundamental signal‐to‐noise ratios, the problem of being able to detect the analyte in the presence of a relatively large background absorption should be able to be overcome with perseverance.
The high sensitivity of the photothermal spectroscopy methods has led to applications for analysis of low absorbance samples. Dovichi (1987
