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More About This Title Photothermal Spectroscopy Methods, Second Edition
English
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.
English
Stephen E. Bialkowski, PhD, is Professor of Chemical Analysis at Utah State University with interests in atmospheric chemistry, spectroscopy, nonlinear optics, and chemometrics.
Nelson G. C. Astrath, PhD, is Associate Professor in the Department of Physics at Universidade Estadual de Maringá with interests in photothermal sciences and light and matter interaction effects.
Mikhail Proskurnin, PhD, is Professor in Analytical Chemistry in the Department of Chemistry at Lomonosov Moscow State University with interests in photonics, analytical spectroscopy, and photothermal spectroscopy in analytical and physical chemistry and applied materials science and biomedical research.
English
About the authors
Preface
Chapter 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
1.5.1 Nature of the photothermal effect
1.5.2 Photoacoustic spectroscopy
1.5.3 Single-beam photothermal lens spectroscopy
1.5.4 Photothermal z-scan technique
1.5.5 Photothermal interferometry
1.5.6 Two-beam photothermal lens spectroscopy
1.5.7 Photothermal lens microscopy
1.5.8 Photothermal deflection, refraction, and diffraction
1.5.9 Photothermal mirror
1.5.10 Photothermal IR-microspectroscopy
1.5.11 Photothermal radiometry
1.5.12 Historic summary
1.6 Some important features of photothermal spectroscopy
Bibliography
Chapter 2: Absorption, Energy Transfer, and Excited State Relaxation
2.1 Factors affecting optical absorption
2.2 Optical excitation
2.2.1 Kinetic treatment of optical transitions
2.2.2 Non-radiative transitions
2.3 Excited state relaxation
2.3.1 Rotational and vibrational relaxation
2.3.2 Electronic states and transitions
2.3.3 Electronic state relaxation
2.4 Relaxation kinetics
2.5 Nonlinear absorption
2.5.1 Multiphoton absorption
2.5.2 Optical saturation of two level transitions
2.5.3 Optical bleaching
2.5.4 Response times during optical bleaching
2.5.5 Optical bleaching of organic dyes
2.5.6 Relaxation for impulse excitation
2.5.7 Multiple photon absorption
2.6 Absorbed energy
Bibliography
Chapter 3: Hydrodynamic Relaxation; Heat Transfer and Acoustics
3.1 Local equilibrium
3.2 Thermodynamic and optical parameters in photothermal spectroscopy
3.2.1 Enthalpy and temperature
3.2.2 Energy and dynamic change
3.3 Conservation equations
3.4 Hydrodynamic equations
3.5 Hydrodynamic response to photothermal excitation
3.5.1 Solving the hydrodynamic equations
3.5.2 Thermal diffusion mode
3.5.3 Fourier-Laplace solutions for the thermal diffusion equation
3.5.4 Propagating mode
3.5.5 Summary of hydrodynamic mode solutions
3.6 Density response to impulse excitation
3.6.1 One dimensional case
3.6.2 Two dimensional cylindrically symmetric example
3.6.3 Coupled solutions
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 3a - Thermodynamic parameter calculation
Appendix 3b - Propagating mode impulse-response for polar coordinates, infinite media
Bibliography
Chapter 4: Temperature Change, Thermoelastic Deformation, and Optical Elements in Homogeneous Samples
4.1 Temperature change from gaussian excitation sources
4.1.1 Thermal diffusion approximation
4.1.2 Gaussian laser excitation of optically thin samples
4.1.3 Short pulse laser excitation
4.1.4 Continuous laser excitation
4.1.5 Chopped laser excitation
4.1.6 On-axis temperature change for periodic excitation
4.1.7 Gaussian Laser Excitation of Absorbing and Opaque Samples
4.1.8 Thermal gratings
4.2 Thermodynamic parameters
4.2.1 Thermodynamic parameters affecting temperature
4.2.2 Convection heat transfer
4.3 Thermoelastic displacement
4.3.1 Continuous Laser Excitation
4.3.2 Short-Pulse Laser Excitation
4.4 Optical elements
4.4.1 Phase shift and optical pathlength difference
4.4.2 Phase shift and optical pathlength difference under thermoelastic deformation
4.4.3 Deflection angle
4.4.4 Thermal lens focal length
4.4.5 Grating strength
4.5 Temperature dependent refractive index change
4.5.1 Density and temperature dependence of refractive index
4.5.2 Population dependence on refractive index
4.5.3 Soret effect
4.5.4 Other factors affecting refractive index
4.6 Temperature change and thermoelastic displacement from top-hat excitation sources
4.6.1 Temperature change from top-hat excitation sources
4.6.2 Thermoelastic displacement from top-hat excitation sources
4.7 Limitations
4.7.1 Excitation beam waist radius changes
4.7.2 Effects of scattering and optically thick samples
4.7.3 Finite extent sample effects
4.7.4 Accounting for finite cell radius
Bibliography
Chapter 5: Photothermal Spectroscopy in Homogeneous Samples
5.1 Photothermal interferometry
5.2 Photothermal deflection
5.2.1 Deflection angle for pulsed laser excitation
5.2.2 Deflection angle for continuous and chopped laser excitation
5.2.3 Deflection angle detection
5.3 Thermal lens focal length
5.3.1 Pulsed excitation thermal lens focal length
5.3.2 Continuous and chopped excitation thermal lens focal length
5.3.3 Focal length for periodic excitation
5.4 Detecting the thermal lens
5.4.1 Signal for symmetric lens
5.4.2 Signal for different x and y focal lengths
5.4.3 Lock-in amplifier or pulse height detected signal
5.4.4 Signal development with large apertures
5.4.5 Signal development based on image analysis and other optical filters
5.5 Types of photothermal lens apparatuses
5.5.1 Single-laser apparatus
5.5.2 Differential single-laser apparatus
5.5.3 Two-laser apparatus
5.6 Two-laser photothermal lens spectroscopy
5.6.1 Excitation wavelength dependence in two-laser photothermal spectroscopy
5.7 Differential two-laser apparatuses
5.8 Diffraction effects
5.8.1 Probe laser diffraction effects for pulsed excitation
5.8.2 Probe laser diffraction effects for continuous excitation
5.8.3 Diffraction effects for single laser photothermal lens
5.8.4 Effect of diffraction on the thermal lens enhancement factor
Bibliography
Chapter 6: Analytical Measurement and Data Processing Considerations
6.1 Sensitivity of photothermal spectroscopy
6.1.1 Photothermal lens enhancement factors
6.1.2 Relative sensitivity of photothermal lens and deflection spectroscopies
6.1.3 Relative sensitivity of photothermal lens and photothermal interferometry spectroscopies
6.1.4 Relating photothermal signals to absorbance and enhancement
6.1.5 Intrinsic enhancement of two-laser methods
6.1.6 Enhancement limitations
6.1.7 The choice of solvents for photothermal lens measurements
6.2 Optical instrumentation for analysis
6.2.1 Dynamic reserve
6.2.2 Differential measurements
6.2.3 Spectroscopic measurement
6.2.4 Fiber optics
6.3 Processing photothermal signals
6.3.1 Analog signal processing
6.3.2 Digital signal processing
6.4 Photothermal data processing
6.4.1 Excitation irradiance curves
6.4.1 Calibration
6.4.3 Metrological parameters of photothermal lens spectrometry
6.5 Considerations for trace analysis
6.5.1 Unstability of dilute solutions
6.5.2 Sources of losses and contamination
6.5.3 Changes in sensitivity and selectivity due to reaction chemistry at the trace level
6.5.4 Statistical features at the level of low concentrations
6.6 Tracking down and reducing noise
Bibliography
Chapter 7: Analytical Applications
7.1 Areas of analytical application
7.2 Applications to stationary homogeneous samples
7.2.1 Photothermal techniques
7.2.2 Gas phase samples
7.2.3 Liquid samples
7.3 Application to disperse solutions
7.3.1 Nano-sized particles and nanocomposite materials
7.3.2 Analysis of biological samples
7.4 Photothermal spectroscopy detection in chromatography and flow analysis
7.4.1 Temperature change in flowing samples
7.4.2 Deflection angles and inverse focal lengths in flowing samples
7.4.3 Applications in chromatography
7.4.4 Application to flow injection analysis
7.5 Photothermal spectroscopy detection in capillary electrophoresis
7.5.1 Influence of electrophoretic flow rate
7.5.2 Effect of the composition of the background electrolyte solution on the sensitivity
7.5.3 Applications
7.6 Photothermal spectroscopy detection in microanalytical and microfluidic systems
7.7 Determination of parameters of reactions
7.7.1 Determination of Thermodynamic Parameters and Constants
7.7.2 Chemical reaction control and real-time monitoring
7.7.3 Kinetic parameters of reactions
7.8 Excitation and relaxation kinetics
7.8.1 Relaxation kinetics and quantum yield studies
7.8.2 Photodynamic irradiance dependent signal studies
7.8.3 Optical bleaching in organic dye molecules
7.8.4 Optical bleaching effects in pulsed laser photothermal spectroscopy
Bibliography
Chapter 8: Photothermal Spectroscopy of Heterogeneous Samples
8.1 Types of heterogeneity
8.2 Apparatuses for photothermal deflection
8.3 Surface absorption
8.3.1 Thermal diffusion at surfaces
8.3.2 Temperature change from pulsed excitation
8.3.3 Temperature change from continuous excitation
8.3.4 Temperature change from periodic excitation
8.4 Thermal diffusion in volume absorbing samples
8.4.1 Volume temperature change for pulsed excitation
8.4.2 Periodic excitation of volume absorbers
8.5 Temperature change in layered samples
8.5.1 Periodic excitation of layered samples
8.5.2 Pulsed excitation of thick 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
8.13.1 Bulk properties
8.13.2 Solid surfaces
8.14 Applications to chemical analysis
8.14.1 Application to surface determination and optical sensing materials
8.14.2 Applications to gel and thin layer chromatography
8.14.3 Other application to applied chemical analysis
8.14.4 Application to biological analysis
Bibliography
