Molecular and Laser Spectroscopy: Advances and Applications

Molecular and Laser Spectroscopy

Advances and Applications

V.P. Gupta

University of Lucknow, Lucknow, India

University of Jammu, Jammu-Tawi, India

Université de Provence, Marseilles, France

Table of Contents

Cover image

Title page

Copyright

Dedication

List of Contributors

Biography

Preface

Chapter 1. Introduction and Overview

1. Introduction

2. Overview

Chapter 2. Near-IR Spectroscopy and Its Applications

1. Introduction

2. Principles and Advantages of Near-Infrared Spectroscopy

3. Examples of Near-Infrared Spectra

4. Advantages of Near-Infrared Spectroscopy

5. Spectral Analysis in the Near-Infrared Region

6. Quantum Mechanical Methods in Near-Infrared Spectroscopy

7. Instrumentation

8. Selected Applications

Chapter 3. Recent Advances in Sensor Developments Based on Silver Halide Fibers for Mid-Infrared Spectrometric Analysis

1. Introduction

2. Fundamentals of Infrared Fibers

3. Mid-Infrared Fiber-Optic Probes

4. General and Special Applications of Fiber-Optic Probes

5. Conclusions

Chapter 4. Terahertz Spectroscopy: Advances and Applications

1. Introduction

2. Terahertz Instrumentation

3. Experimental Setups

4. Comparison of Terahertz Spectroscopy With Other Spectroscopy Techniques

5. Application of Terahertz Spectroscopy

6. Future Outlook

Chapter 5. Coherent Optical Spectroscopy/Microscopy and Applications

1. Introduction

2. Coherent Optical Spectroscopy/Microscopy

3. Importance of Lasers in Optical Spectroscopy/Microscopy

4. Linear and Nonlinear Spectroscopy/Microscopy

5. Linear Spectroscopy/Microscopy Techniques

6. Nonlinear Spectroscopy/Microscopy Techniques

7. Conclusions

Chapter 6. Applications of Raman and Infrared Microscopy to Materials and Biology

1. Introduction

2. Principles and Instrumentation of Infrared Spectroscopy

3. Principles and Instrumentation of Raman Spectroscopy

4. Conclusion

Chapter 7. Resonance Raman Spectroscopy: Principles and Applications

1. Introduction

2. Raman and Resonance Raman Effect

3. Experimental Setup

4. Applications of Resonance Raman Spectroscopy

5. Recent Applications of Resonance Raman Spectroscopy

6. Conclusions

Chapter 8. Two-Photon Spectroscopy of Organic Materials

1. Introduction

2. Theoretical Background for Two-Photon Absorption Process in Organic Materials

3. Two-Photon Absorption Spectroscopy Techniques

4. Molecular Structure–Two-Photon Absorption Properties Relationship

5. Polarization Effect on the Two-Photon Absorption Spectroscopy

6. Summary and Future Scope

Chapter 9. Femtosecond Stimulated Raman Spectroscopy

1. Introduction

2. Theoretical Background on Femtosecond Stimulated Raman Spectroscopy

3. Conventional Optical Layout for Femtosecond Stimulated Raman Spectroscopy Signal Detection

4. Applications of Femtosecond Stimulated Raman Spectroscopy to Chemistry and Biology

5. Summary and Future Scope

Chapter 10. 2D Correlation Spectroscopy and Its Application in Vibrational and Optical Spectroscopy

1. Introduction

2. Background of Two-Dimensional Correlation Spectroscopy

3. New Developments on Two-Dimensional Correlation Spectroscopy

4. Applications of Two-Dimensional Correlation Spectroscopy

5. Concluding Remarks

Chapter 11. Laser Spectroscopy and Lasing Actions in Nanomaterials

1. Introduction

2. Laser Spectroscopy of Nanomaterials

3. Time-Resolved Spectroscopy of Nanomaterials

4. Lasing Action in Nanomaterials

5. Ultrafast Pump–Probe Spectroscopy of Nanomaterials

Chapter 12. Laser-Induced Breakdown Spectroscopy: Advanced Analytical Technique

1. Introduction

2. Theoretical Details

3. Calibration Models

4. Experimental Details

5. Applications

Chapter 13. Photoacoustic Spectroscopy: Applications in Security and Biology

1. Introduction

2. Radiative and Nonradiative Transitions in Molecules

3. Experimental Methods in Photoacoustic Spectroscopy

4. Photoacoustic Detection of Harmful Chemicals

5. Hyperspectral Imaging and Photoacoustic Spectroscopy

6. Conclusion

Chapter 14. Matrix Isolation Spectroscopy—A Window to Molecular Processes

1. Introduction

2. Matrix Isolation Infrared Setup

3. Conformational Studies

4. Weak Intermolecular Interactions

5. Photochemical Processes in the Matrix

6. Ions and Neutral Metal Clusters

7. Laser Ablation Matrix Isolation

8. Species With Unusual Oxidation States

9. Role of Computational Chemistry

10. Other Experimental Techniques to Probe Matrix-Isolated Species

Index

Copyright

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Notices

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Dedication

Dedicated to the loving memory of my beloved parents Dr. D.P. Gupta and Smt. Ram Kali.

Anything good that has come to my life has been because of your example, guidance, and love.

List of Contributors

Krzysztof B. Beć,     Kwansei Gakuin University, Hyogo, Japan

Chet R. Bhatt

Mississippi State University, Starkville, MS, United States

National Energy Technology Laboratory (NETL), Pittsburgh, PA, United States

Joydeep Chowdhury,     Jadavpur University, Kolkata, India

Nicola Coluccelli,     IFN-CNR, Politecnico di Milano, Milano, Italy

Jyotishman Dasgupta,     Tata Institute of Fundamental Research, Mumbai, India

Leonardo De Boni,     Universidade de São Paulo, São Carlos, Brazil

Sven Delbeck,     South-Westphalia University of Applied Sciences, Iserlohn, Germany

Pankaj Dubey,     Indian Institute of Science Education & Research, Mohali, Punjab, India

Yashashchandra Dwivedi,     National Institute of Technology Kurukshetra, Haryana, India

Rekha Gautam,     Indian Institute of Science, Bangalore, India

Charles T. Ghany,     Mississippi State University, Starkville, MS, United States

V.P. Gupta Editor 

University of Lucknow, Lucknow, India

University of Jammu, Jammu-Tawi, India

Université de Provence, Marseilles, France

H. Michael Heise,     South-Westphalia University of Applied Sciences, Iserlohn, Germany

Christian W. Huck,     Leopold-Franzens University, Innsbruck, Austria

Young M. Jung,     Kangwon National University, Chunchon, Korea

Ginny Karir,     Indian Institute of Science Education & Research, Mohali, Punjab, India

Shreetama Karmakar,     Tata Institute of Fundamental Research, Mumbai, India

Vikas Kumar,     IFN-CNR, Politecnico di Milano, Milano, Italy

Lukas Küpper,     Infrared Fiber Sensors, Aachen, Germany

Dustin L. McIntyre,     National Energy Technology Laboratory (NETL), Pittsburgh, PA, United States

Cleber R. Mendonça,     Universidade de São Paulo, São Carlos, Brazil

Anamika Mukhopadhyay,     Indian Institute of Science Education & Research, Mohali, Punjab, India

Isao Noda,     University of Delaware, Newark, DE, United States

Yukihiro Ozaki,     Kwansei Gakuin University, Hyogo, Japan

Dario Polli

IFN-CNR, Politecnico di Milano, Milano, Italy

CNST, Istituto Italiano di Tecnologia, Milano, Italy

Shriganesh S. Prabhu,     Tata Institute of Fundamental Research, Mumbai, India

Palas Roy,     Tata Institute of Fundamental Research, Mumbai, India

Jyoti Saini,     Indian Institute of Science Education & Research, Mohali, Punjab, India

Sanchita Sil,     Defence Bioengineering & Electromedical Laboratory, Bangalore, India

Jagdish P. Singh

Mississippi State University, Starkville, MS, United States

JPS Advanced Technology R&D LLC, Starkville, MS, United States

Surya N. Thakur,     Benares Hindu University, Varanasi, India

Siva Umapathy,     Indian Institute of Science, Bangalore, India

Kanupriya Verma,     Indian Institute of Science Education & Research, Mohali, Punjab, India

K.S. Viswanathan,     Indian Institute of Science Education & Research, Mohali, Punjab, India

Marcelo G. Vivas,     Universidade Federal de Alfenas, Poços de Caldas, Brazil

Yizhuang Xu,     Peking University, Beijing, China

Fang Y. Yueh

Mississippi State University, Starkville, MS, United States

JPS Advanced Technology R&D LLC, Starkville, MS, United States

Biography

Professor V.P. Gupta, born in December 30, 1942, obtained Ph.D. degree from Moscow, USSR, in 1967. He has been Professor Emeritus and also the Principal Investigator of DST Book-Writing Project under USERS (Utilization of Scientific Expertise of Retired Scientists) scheme at the University of Lucknow, Lucknow. Professor Gupta has 45 years of experience in teaching and research at several universities. He has been Professor and Chairman of the Department of Physics at the University of Jammu, Jammu-Tawi, India, a Visiting Professor of Chemistry at the Université de Provence, Marseilles, France and Professor of Physics at the University of Calabar, Nigeria. He has the distinction of being Professor Emeritus, University Grants Commission (UGC), India, Emeritus scientist of the Council of Scientific & Industrial Research (CSIR), India, and the All India Council of Technical Education (AICTE), New Delhi, India. He was a visiting scientist/fellow at the University of Helsinki, Helsinki, Finland, and at International Centre for Theoretical Physics, Trieste, Italy; and a member of several national and international academic bodies. Over the past four decades, he has successfully executed several major and minor scientific research projects granted by the national funding agencies such as Department of Science & Technology (DST), Government of India, New Delhi; UGC, New Delhi; CSIR, New Delhi; AICTE, New Delhi; and Indian Space Research Organization (ISRO), Bangalore. His major areas of research are molecular spectroscopy and molecular structure, quantum chemistry, matrix isolation infrared studies, astrochemistry, and laser spectroscopy. He has to his credit 99 research publications and 3 books, including the book published by Elsevier, Waltham, United States - Academic Press, in October 2015.

Preface

While the progress in science is dependent on two vital factors, that is, generation of knowledge and its successful transfer through the scientific information media, a close interaction between the two is equally important. Printing alone does not lead to successful growth in knowledge. In fact, the excess of it may prove to be counterproductive and confusing unless it is properly interpreted. The real growth in knowledge can only be achieved through a process of identifying, sieving, and formulating the probable key ingredients out of the data, theories, and concepts that are reported in research journals whose number has seen a substantial growth in recent past. Review articles surveying advancements in all the developing areas of molecular and laser spectroscopies appear in scientific journals from time to time. However, for people who have no advanced knowledge of the subject, it is often difficult to find a coherent representation of the basic principles and the advances in the various areas from the many articles spread over many journals. Keeping this fact in mind, this book lays emphasis on the complete development of the subject in a booklike fashion, so as to bridge the gap between a text book and advanced review articles, with the prime focus on imparting updated information to the readers. It provides a solid grounding in the fundamentals of many aspects of molecular spectroscopy, and linear and nonlinear laser spectroscopy. Starting from the basics and fundamental principles, it develops the subject in a systematic and authentic manner and goes on to describe the latest advancements, both in terms of techniques and applications, and highlights the future projections. Our objective is to present the most cutting-edge topics in an engaging and understandable manner by providing the necessary background information for better understanding of the inquisitive reader. The background information should help the readers to focus and channelize their efforts on more specialized topics in laser and molecular spectroscopy.

While a review of the recent advances in major areas of molecular spectroscopy and laser spectroscopy/microscopy has been carried out in this book, it is in no way complete. The topics covered include advances in near-infrared (NIR), mid-infrared (MIR), and terahertz spectroscopy, Raman spectroscopy/microscopy, and fluorescence spectroscopy. Both the linear and nonlinear processes reflected in the infrared and Raman spectra are included. Topics such as linear and nonlinear spectroscopy/microscopy techniques, laser-induced fluorescence (LIF) spectroscopy/microscopy, coherent Raman spectroscopy (CRS)/microscopy, resonant and surface-enhanced Raman scattering (SERS), laser spectroscopy of nanomaterials, laser-induced breakdown spectroscopy (LIBS), time-resolved and ultrafast femtosecond spectroscopy, two-photon absorption spectroscopy, photoacoustic spectroscopy (PAS), and matrix isolation infrared and Raman spectroscopy are included in this book. In view of the advantages provided by chemometrics and two-dimensional (2D) correlation spectroscopy in the in-depth mathematical analysis of the spectral data, and their increasing application in simplification of complex spectra, enhancement of spectral resolution, and correlation of measurements between closely related or completely different types of techniques, a chapter on 2D correlation spectroscopy has also been included. Improvements in instrumentation and the development of new techniques have greatly enhanced each field in imaging, sensing, and understanding fundamental chemical principles. Each one has certain advantages and limitations that confine them to certain disciplines. In some cases, these limitations have been overcome for future applications. Applications of laser spectroscopy constitute a vast field, and it is difficult to cover it comprehensively in a single review. As such, examples have been chosen from a variety of fields to illustrate the new developments and the power of applied laser spectroscopy.

The book has contributions from experts of different academic institutions in Austria, Brazil, China, Germany, India, Italy, Japan, Korea, and the United States of America, giving it a global scientific flavor in terms of scientific approaches and methodologies. No attempt was made by the editor to suppress the individuality of the different contributors. As such, minor overlap in the subjects discussed in different articles is unavoidable. However, this has its own advantages as the reader is confronted with the issues from different points of view, leading to a deeper insight.

I would like to extend my gratitude to all the contributors for their efforts in preparing the manuscripts and meeting the timelines. I would also like to express my appreciation for my colleagues who have helped me in the final selection of topics for this book and giving it the final shape. In addition, in a very special and personal way, I acknowledge the pivotal role of my wife, Madhu, who has been a perennial source of inspiration behind this endeavor. Her continued encouragement, support, love, and understanding have helped me in a big way in the successful execution of this work. I also appreciate my children and grandchildren, Manjari, Vikas, Ashish, Nidhi, Pulkit, Divayum, and Shubhang, for their constant motivation and emotional support during this interesting endeavor. I am hopeful that this book will prove to be an intellectual treat for our readers who would enjoy and appreciate this ensemble of chapters.

V.P. Gupta

Editor

Chapter 1

Introduction and Overview

V.P. Gupta Editor 

Abstract

Several developments have taken place in the recent past in the field of molecular and laser spectroscopy, which have found newer applications in diverse areas ranging from materials to medicines and defence—touching lives in all its hues. Lasers have greatly enriched the science of atoms and molecules, both by adding novel spectroscopic techniques and by reviving some old ones. These involve both linear and nonlinear processes reflected in the infrared and Raman spectra and the time-resolved spectroscopy. The integration of a microscope to a spectrometer and the development of fast spectroscopic imaging by infrared and Raman imaging techniques have allowed spatially resolved spectroscopy of large or multiple samples, enhancement of spatial resolution, and the investigation of molecular dynamics and biological mechanisms. Some of these advancements have been discussed in the present book. This chapter provides a concise overview of the book and the contents of its various chapters, which include recent advances in theory, instrumentation/experimental techniques, applications, limitations, and the future outlook of the spectroscopic techniques.

Keywords

2D correlation spectroscopy; Femtosecond spectroscopy; Fiber-optic probes; Infrared; Laser spectroscopy; Laser-induced breakdown spectroscopy; Linear and nonlinear spectroscopy; Matrix isolation spectroscopy; Microscopy; Molecular spectroscopy; Nanomaterials and random lasers; Photoacoustic spectroscopy; Raman, Resonance spectroscopy; Two-photon absorption; Waveguides

Chapter Outline

1. Introduction

2. Overview

2.1 Near-Infrared Spectroscopy

2.2 Mid-Infrared Spectroscopy

2.3 Terahertz Spectroscopy (0.2 to 30THz)

2.4 Linear and Nonlinear Raman and Infrared Spectroscopy and Microscopy

2.5 Resonance Raman Spectroscopy

2.6 Two-Photon Absorption Spectroscopy

2.7 Femtosecond Raman Spectroscopy

2.8 Two-Dimensional Correlation Spectroscopy

2.9 Laser Spectroscopy of Nanomaterials

2.10 Laser-Induced Breakdown Spectroscopy

2.11 Photoacoustic Spectroscopy

2.12 Matrix Isolation Spectroscopy

Reference

1. Introduction

One of the most exciting challenges in modern science has been to unravel the detailed code of molecular spectra because this code speaks directly of a molecule's energy levels. Chemical systems undergoing a change display spectral signatures in various regions of the electromagnetic spectrum. The details of these signature codes recorded in terms of the molecular spectra can be deciphered to get information about the related molecular structures and dynamic processes in the electronic ground and excited states. The study of fundamental regularities in the electronic (absorption, fluorescence, and phosphorescence), vibrational (both infrared and Raman), rotational, and hyperfine spectra has established their relation with molecular structure. They reveal not only the structural characteristics of molecules but also the strength of the bonding potential between atoms, not only for the ground state but also for the electronically excited states, and for unstable short-lived molecules. In particular, techniques based on vibrational spectroscopy have been widely used in all areas of science to provide a close understanding of the composition of materials at the molecular level. The field of molecular spectroscopy has continued to advance rapidly with measurements in a variety of molecules with increasing resolution, which lead to the observation of new effects and continued improvements in the theoretical description of the spectra. This expansion resulted from both improvements in existing instrumentation and the development of new techniques in the fields of Raman and infrared (IR) spectroscopy. Matrix isolation IR and Raman spectroscopy has been one such effort at developing a technique that, as a means of trapping reactive species, such as radicals, and unstable and transient species, allows for an extended lifetime of these species. This experimental technique offers advantages of sharp spectral linewidths and removal of spectral congestion, thereby leading to simple, highly resolved spectral features. Efforts have continued toward increasing spectral resolution and improved detection techniques. The replacement of dispersion technique used in grating or prism spectrographs by interferometry and Fourier transform (FT) analysis, as used in FT infrared (FTIR) spectrometers, has enhanced spectral resolution from 1 to 0.01  cm−¹. As an essential tool in establishing the nature of substances, molecular spectroscopy has expanded into new and exciting areas such as material science, biology, medical diagnostics, environmental science, industrial process control, homeland security, and space exploration.

Since the development of lasers, the conduct of the entire field of molecular spectroscopy has undergone major and far-reaching qualitative changes. Laser radiation is finding many applications for analysis and diagnostics based on the wavelength-dependent interaction between electromagnetic radiation and matter. Laser techniques have greatly enriched the science of atoms and molecules, both by adding novel spectroscopic techniques and by reviving some old ones. These involve both linear and nonlinear processes reflected in the IR and Raman spectra. The impact of lasers on spectroscopy can hardly be overestimated. With the use of even low-powered laser sources, such as semiconductor diode laser, which results in linear processes, it is now possible to have the advantages of high spectral resolution, supersensitive and superfast detection, remote sensing, etc. Many experiments, which could not be done before the application of lasers, because of lack of intensity or insufficient resolution, are now readily performed with lasers. While the narrow bandwidth of modern tunable lasers makes its interaction with free atoms and molecules having sharp spectral features extremely selective, the high spectral intensity available with pulsed as well as continuous-wave lasers increases the sensitivity and makes the detection of single atom or molecule possible. This represents the ultimate sensitivity in analytical chemistry.

From its beginning, laser spectroscopy has far surpassed conventional spectroscopic techniques in sensitivity, resolution, and measurement accuracy, and we are witnessing unabated progress in all the three directions. Laser spectroscopy provides the practical means of studying the spectra of short-lived molecules, such as transient molecules, free radicals, and molecular ions, which were impossible to be studied by conventional spectroscopy because of low sensitivity and slow scanning speed. Because of their extremely small bandwidth, single mode lasers allow a spectral resolution, which far exceeds that of conventional spectrometers. In recent years, the development of precisely controlled tunable narrow linewidth laser sources with appreciable power has provided powerful tools for the measurement and analysis of molecular spectra. In many cases the tunable lasers replace wavelength-selecting elements such as spectrometers and interferometers. With the advent of very short laser pulses, it has now been possible to conduct observations in timescales that are not only shorter than individual vibrational lifetimes or dephasing times but also shorter than vibrational oscillation periods. This has led to the development of the area of time-resolved spectroscopy. Using very short laser pulses, it is now possible to conduct observations in nano-, pico-, and femtosecond timescales. With such short pulses, it has been possible to track a chemical reaction and record each bond-forming and/or bond-breaking event. Femtosecond time-resolved spectroscopy therefore recreates the whole chemical event as a series of snapshots as if the dynamic process was frozen in time. Femtosecond Raman spectroscopy has proved to be a useful tool to probe evolution of molecular systems in the electronic excited state. Such vibrational spectroscopy is well suited for the study of excited electronic states, radical reactions, electron transfer, and vibrational dynamics. Molecular structures corresponding to unstable intermediates between the reactant and the product, crystal structure during phase transition, etc. have now been observed using femtosecond laser pulses. Fortunately, the relationship between laser spectroscopy and conventional molecular spectroscopy is not one of replacement but of complementarity, which makes laser spectroscopy an inseparable part of modern molecular spectroscopy.

Far-reaching changes have also come about in the instrumentation techniques in the near-IR (NIR) and mid-IR (MIR) regions with the development of intense laser sources, such as semiconductor diode lasers, room temperature–operated quantum cascade lasers (QCLs), and optical parametric oscillators, and detectors. Sophisticated instruments that provide spatial resolution beyond diffraction limit, fiber-optic probes, waveguides, miniature and highly integrated spectrometers, and low-cost FTIR minispectrometers with a size similar to a small sheet of paper are now on the way. Different accessories can be attached to these spectrometers for transmission or attenuated total reflection (ATR) measurements, making them attractive for various purposes. By combining with fiber-optic probes, the reach of the spectrometer can be tremendously extended. The flexibility of optical fibers used as waveguides permits probes to be applied within inaccessible sites and very small spaces. It also allows centralization of a spectrometer and analysis devices at a distance from the actual measurement and provides the option of multiplexing several probes. A wide variety of fiber-optic probes and configurations have now been developed, which allow IR radiation to be delivered to diverse environments outside the laboratory. In particular, flexible fiber probes based on silver halide material have several advantages, because they allow remote sensing with a fast and easy sample measurement within the NIR and MIR wavelength regions from 3 to 20  μm. A special class of systems, micro-opto-electro-mechanical systems (MOEMS) combining micro-electro-mechanical, optical, and electrical systems, present a significant step forward in the development of smart spectroscopic sensors, microsystem technology, and vibrational spectroscopy instrumentation.

QCLs from MIR to the terahertz spectral range represent a relatively recent development in the area of semiconductor lasers and have concrete impact in many technological applications such as trace gas analysis, optical communications, and real-time imaging. QCLs can generate short pulses with pico- and femto-second durations and have found application in time-resolved spectroscopy. Earlier MIR semiconductor lasers such as diode lasers were based on interband transitions, whereas QCLs utilize intersubband transitions. The photon energy, and also the wavelength of transitions, can be varied in a wide range by engineering the details of the semiconductor layer structure. Unlike diode lasers, QCLs can easily be designed to emit at multiple and widely differing wavelengths, and broadband tuning has been realized by using, for example, an external cavity (EC) grating as a wavelength-defining element. A spectral range of about 1000  cm−¹, including the most informative spectral fingerprint region, can thus be covered by multimodule EC-QCLs. Spectrometers with EC-QCLs have been suggested for clinical chemistry applications in quantitative blood substrate assays. Spectacular developments have taken place in imaging of cells and tissues using FTIR spectrometers with focal plane arrays and nanoscopy-based on NIR spectroscopy with spatial resolution similar to tip-enhanced Raman spectroscopy (TERS). Microscopes with QCLs have been developed and are now commercially available for spectral histopathology.

The spectroscopic technique that arises due to the inelastic scattering of light discovered by the Indian scientist Sir C.V. Raman in 1928 and named after him as Raman Spectroscopy has transcended all its barriers and has emerged as a technology that has wide applications in all the areas ranging from materials to medicines. It can be reckoned as a serious contender among all the other analytical tools because of its noninvasive and nondestructive nature. The Raman and IR transitions are like the two sides of a coin that provide complementary information. Development of lasers has resulted in the growth of areas of spontaneous Raman scattering and nonlinear Raman spectroscopies such as coherent anti-Stokes Raman scattering (CARS), resonance Raman scattering (RRS), surface-enhanced Raman scattering (SERS), stimulated Raman spectroscopy (SRS), and two-photon excitation fluorescence spectroscopy. Major advantage of these methods over the conventional Raman spectroscopy is the ability to obtain Raman spectra with very high resolution, which is solely determined by the linewidth of the input sources. High-resolution measurements utilizing these techniques preclude the necessity of using monochromators, interferometers, or other apparatuses usually used in conventional Raman spectroscopy. Applications of Raman spectroscopy saw new heights after the discovery of SERS, which enabled analyses of analytes at ultratrace levels pushing the limit of detection to single-molecule level. This advantage along with high signal-to-noise ratio offered new possibilities for Raman spectroscopy to be used as a sensitive analytical technique. Furthermore, following the discovery of lasers, significant advancements have taken place in an area such as photoacoustic spectroscopy (PAS), which although discovered about a century back could not find much practical application for want of a strong light source.

During the past decade, the integration of a microscope to a spectrometer has pushed the limits of the spectroscopic techniques to collect specific information from diffraction limited spots. A one-to-one mapping of the investigated volume of the sample constitutes a microscopic image. Much improved signal efficiency obtained by using lasers and availability of high-performance multichannel detectors, optimization of data acquisition, and the development of efficient evaluation and representation software have enabled several such techniques for high-speed microscopy, few of them up to video-rate imaging, and two-dimensional (2D) and three-dimensional (3D) mapping. The fast spectroscopic imaging by IR and Raman imaging techniques allows spatially resolved spectroscopy of large or multiple samples, enhancement of spatial resolution due to retention of radiation throughput, and the investigation of molecular dynamics and biological mechanisms. On the basis of their unique characteristics and capabilities, optical spectroscopy/microscopy techniques have got a variety of important applications in material science, biology, pharmaceutical, and medical fields. Raman imaging aims at separating molecular species present in the sample on the basis of their spectral differences, which is reflected in the 2D maps. Nonlinear techniques have been used to provide inherent 3D sectioning.

Although initially the terahertz region (frequency range 0.2 to 30  THz; 1  THz  =  10¹²  Hz) lying between the IR and microwave regions of the electromagnetic spectrum remained to be one of the least tapped regions of the electromagnetic spectrum, most probably due to the difficulty in generating and detecting the THz radiation, it has now become one of the extremely important regions. It has found several potential applications in condensed matter systems, material science, chemicals and pharmaceuticals, medical diagnostics (including imaging in biomaterial identification), agriculture, high-bandwidth short-distance secure communication/data transfer, and defense, mainly due to its nondestructive, nonionizing material evaluation properties. Intense research activities are taking place in the development of strong and broadband THz sources and detectors and of suitable materials for THz optics and in finding its newer applications.

During the last two decades, significant advancements have also taken place in some other fields of molecular spectroscopy such as multiphoton (in particular, two-photon) absorption spectroscopy, laser spectroscopy of nanomaterials, and laser-induced breakdown spectroscopy.

Multiphoton processes involve the concerted interaction of two or more photons with individual atoms or molecules; the most widely studied cases involve two-photon interactions. Two-photon absorption (2PA) spectroscopy measures the wavelength-dependent cross sections for simultaneously absorbing two photons that are individually nonresonant with the electronic transitions of a molecule. Two photons are simultaneously absorbed from the intense pump beam to promote the molecule to an excited state. Because there are different symmetry-selection rules for one- versus two-photon excitation, it is sometimes possible to access different excited states using the two methods. Since 2PA presents a third-order process several orders of magnitude weaker than linear absorption at low light intensities, its observation is only possible if high light irradiances, in general on the order of a few GW/cm², are used. Until the 1980s, 2PA found great utility only as a spectroscopic tool. A comparison between the one-photon absorption and two-photon absorption spectra of different organic molecules was used as a powerful technique to investigate and understand at the molecular level the relationship between the molecular structure and electronic and optical properties of novel materials and to measure the nonlinear optical response in organic materials. However, more recently it started finding practical applications in several new areas. Thus, some of the features of 2PA spectroscopy have been exploited for the development of optical devices such as 3D optical data storage, fluorescence imaging, photodynamic therapy, frequency upconverted lasing, optical logic, autocorrelation, pulse reshaping, optical power limiting, coherent control, microfabrication, and micromachining. Laser scanning microscopy employing two-photon excitation has become the imaging choice for studying physiological functioning in highly light scattering brain tissue. The focal excitation resulting from the absorption of two photons provides inherent 3D resolution without the need for a confocal pinhole and free of background fluorescence. Multiphoton spectroscopy with polarization control has found potential application for identifying the nature of the excited states and molecular structure of randomly oriented chromophores.

Intense research activities are taking place in the field of nanomaterials, and considerable progress has been made in the sophistication of creation of nanomaterials and nanostructures. The fundamental of nanotechnology lies in the fact that properties of materials change dramatically when their size is reduced to the nanometer range. These materials have attracted special attention due to their peculiar optical properties caused by quantum confinement when one or more of the dimensions are comparable to the exciton Bohr radius. Optical properties are among the most fascinating and useful properties of materials. They are intimately related to other properties and functionalities (e.g., electronic, magnetic, and thermal) that are of fundamental importance to many technological applications, such as energy conversion, chemical analysis, biomedicine, optoelectronics, communication, and radiation detection. Nanosize-structured materials are reported to exhibit interesting luminescent properties, in particular, emission intensity, emission shifting, radiative lifetime, and improved quantum efficiencies. These are quite different from their bulk counterparts. Thus, photoluminescence observed in a semiconductor by optical excitation is quite different from that in the organic material. The optical properties of nanomaterials have been extensively studied using a variety of optical spectroscopic techniques such as ultraviolet–visible (UV-Vis), FT-IR, Raman, and dynamic scattering, which have also been used to understand their chemical and structural properties. Laser spectroscopy techniques such as laser-induced fluorescence, time-resolved spectroscopy, and ultrashort pump–probe spectroscopy have also been used to characterize nanomaterials. The optical properties of nanomaterials may further be manipulated by creating various nanostructures in which degrees of freedom of electron propagation may be controlled (e.g., tetrapod, comb, cone, etc.). Quantum confinement brings ability to tune color with bandgap, improve absorption and emission cross section, etc. Higher absorption and emission cross section and special design of nanocavity and higher plasmon field lead to lasing action in various nanomaterials. One of the unconventional lasing actions reported in nanomaterials is random lasing. Random lasers have been realized in various material systems, from semiconductor nanoparticles and ceramic powder to polymers, organic materials, and biological tissues. All these aspects of nanomaterials are currently receiving considerable attention.

Laser-induced breakdown spectroscopy (LIBS), also called laser-induced plasma spectroscopy (LIPS), is a spectroscopic method based on the spectral and time-resolved analysis of atomic and ionic emission spectra from laser-produced plasma plumes of a sample, which could be solid, liquid, gas, or colloid. Because only a few nano- or picograms of sample is vaporized, it is a relatively noninvasive technique and has been extensively used for the identification and quantification of different elements in ores, alloys, soils, aerosols, and many other liquid samples. It has also been used for multielemental determination in energetic materials, propellants, and military explosives; nuclear materials; and rare earth elements. As one of the fastest analytical techniques in industry, it has found diverse applications in areas of space exploration, environmental monitoring, forensic investigations, and biomedical research. Recent advancements have been made in the application of LIBS in food science for the identification of elements and estimating their concentration in food materials.

Along with the experimental spectroscopic techniques, several important developments have taken place in the mathematical techniques of analysis of spectral data, such as chemometrics and 2D correlation analysis (also known as 2D correlation spectroscopy or 2DCOS). Chemometrics uses mathematical and statistical methods to improve understanding of chemical information and correlate quality parameters or physical properties to analytical instrument data. It has become an essential part in the modern chemical and biomedical fields. 2DCOS is a mathematical technique that is used to study changes in measured signals under perturbations. Developed in 1986 by Isao Noda, 2DCOS has now become a powerful and versatile technique in the form of generalized 2DCOS for the in-depth analysis of spectral data in a variety of spectroscopic probes, such as IR, NIR, Raman, vibrational optical activity, UV-Vis, fluorescence, X-ray, and NMR, obtained under external perturbations such as mechanical, electrical, thermal, chemical, and biological. It is being widely used in various spectroscopic experiments to determine the in-phase and out-of-phase events, the sequence of spectral changes, inter- and intramolecular interactions, and band assignments of reacting groups and to detect correlations between spectra/measurements of different techniques.

From the aforesaid, it is evident that spectroscopy is no doubt the most important tool that has taught us most about the nature of atoms and molecules and is finding increasing applications in various fields. It is also increasingly evident that the variety of spectroscopic work is now such that few workers in the field can deal directly with more than a limited part of it. On the other hand, one needs to maintain contact with other branches than his/her own, not only to follow advances in techniques, but also because of a common interest in atomic and molecular energy levels and the information derived from them. This explains the need for periodic authoritative surveys on recent progress in different branches of molecular and laser spectroscopy.

In a review [1] on the progress in the field of Raman spectroscopy, Nafie has attributed the continuous all-round growth in this field in part to the following factors: (1) progress in techniques for the creation of nanomaterials and nanostructures for which Raman is an excellent probe, (2) refinement of our understanding of SERS as a photonic probe of molecules and materials, (3) improved instrumentation for Raman imaging, including Raman microscopy and TERS, (4) effectiveness of Raman for biomedical imaging and disease diagnosis to complement and enhance current clinical practices, (5) advances in the design and control of ultrafast lasers for applications exploiting nonlinear Raman processes, (6) improvements in Raman instrumentation, and (7) 2D correlation and chemometric analysis of spectral data. Similarly, significant advancements are also currently taking place in the areas of terahertz spectroscopy/microscopy, NIR and MIR spectroscopy, and microscopy which have been finding applications in diverse areas ranging from materials to medicine and defense and touching lives in all its hues. Recent developments in all these and related areas in experimental molecular and laser spectroscopy/microscopy together with the mathematical techniques of analysis of spectral data, such as 2D correlation analysis and chemometrics, have therefore been included in this book.

2. Overview

To provide a concise overview of the book, the contents of its various chapters are highlighted below. These include recent advances in theory, instrumentation/experimental techniques, applications, limitations, and the future outlook of the spectroscopic techniques.

2.1. Near-Infrared Spectroscopy

In Chapter 2, Ozaki, Huck, and Beć have introduced the state-of-the-art NIR spectroscopy and have reviewed its advances in the recent past. The development of FT NIR spectrometers and handheld spectrometers, detectors (single and multichannel), computers, and spectral analysis methods, such as chemometrics, 2D correlation analysis, and quantum chemical calculations (such as post-HF (coupled cluster), DFT, perturbation-corrected vibrational SCF (PT2-VSCF), and generalized VPT2 approach (GVPT2)) of the NIR spectra, have expanded the application of NIR from food and agricultural engineering to chemical, polymer, and petroleum industries, pharmaceutical industry, biomedical sciences, and environmental analysis. These have been included in the review. Advances in NIR imaging, portable and handheld spectrometers, online monitoring, PAT (process analysis technology), and medical diagnosis have been reviewed. The breakthrough in NIR imaging technique has happened during the past decade thanks to the advent of high-performance multichannel detectors, integration of spectrometer and microscope, optimization of data acquisition, and the development of efficient evaluation and representation software. Advanced technologies employing ATR–based miniaturized handheld IR devices using the recently developed MOEMS or miniature diode array systems, capable of efficient analysis of solid and liquid samples, have also been reviewed. The application of NIR spectroscopy and NIR imaging in selected disciplines such as medicinal plants, foods, pharmaceutical, polymers, and biomedical applications has been discussed with examples.

2.2. Mid-Infrared Spectroscopy

Several novel developments in instrumentation in MIR spectroscopy have recently taken place in terms of laser sources, detectors, waveguides, miniaturization of spectrometers, Fabry–Perot interferometers, etc. Heise and coworkers review in Chapter 3 some recent advances in the development of fiber-optic probe instrumentation based on IR transparent polycrystalline silver halide fibers for MIR spectrometric analysis, which is also suitable for process monitoring and quasicontinuous measurements. Sensing elements with signal amplification, attenuated total reflection measurement technique, and novel developments with coupling to QCLs have also been discussed. The fiber material allows replacement of conventional bulky spectrometer accessories by simple fiber-optic probes using transmission, diffuse, or ATR techniques. Some fundamental aspects about the chemical composition, microcrystalline structure, optical characteristics such as absorption and scattering, etc. of such fibers that are important for sensor design are presented. Advances in the quality of silver halide fibers and their extrusion with different cross sections that enable construction of inert sensor probe heads and well suited for process monitoring, and quasicontinuous measurements have been discussed. Probes made solely from fiber material or by coupling fibers to other optical elements such as microprisms from extremely inert diamond can be used for aggressive and corrosive media, as well as for high-pressure and high-temperature applications. These probes exclusively used for attenuated total reflectance measurements have been considered. While transmission and attenuated total reflection techniques have been employed for the analysis of liquids, the spectra of powders can also be best recorded by ATR. A large number of important applications in process analysis chosen from different industrial areas that can be handled by fiber-optic probes and IR spectroscopy have been presented in the chapter. Applications to chemistry (recording spectra of solids and liquids), reaction/process monitoring in industries, clinical and biomedical applications, and development of analytical methods for environmental studies have been considered.

2.3. Terahertz Spectroscopy (0.2 to 30  THz)

Rapid developments have been taking place in the field of THz spectroscopy as may be inferred from the fact that roughly every 3  years the research papers on THz instrumentation and applications are doubling. Intense research efforts are currently taking place to develop broadband, narrow-bandwidth, and high-power THz sources as well as to develop highly sensitive THz radiation detectors or sensors with broadband sensitivity. Major efforts are also being made on the development of different suitable materials for THz optics such as THz quarter- and half-wave plates and THz polarizers. The emerging field of metamaterial has helped in the designing of THz optical components, such as sensors based on split ring resonators. High-resolution imaging in the THz region has also made significant advances. Because imaging provides more information about the shape and structure, and spectroscopy provides more information about the chemical composition, the successful application of THz seems to be a combination of the two. All such research activities have been reviewed by Prabhu in Chapter 4, which also considers application of THz spectroscopy/microscopy to pharmaceuticals, bacterial detection, and identification of living organisms and agriculture.

2.4. Linear and Nonlinear Raman and Infrared Spectroscopy and Microscopy

Optical spectroscopy, in particular vibrational spectroscopy-based technologies, have seeped in all the areas of science and have provided a new dimension in understanding material compositions with molecular specificity. Furthermore, the integration of a microscope to the spectrometer has considerably increased the limits of these spectroscopic techniques to collect specific information from diffraction-limited spots. In particular, imaging by means of Raman spectroscopy has emerged as a powerful technique in the study of structure and various chemical processes occurring in materials and biology. This technique is noninvasive, label free, and capable of providing molecular identity and can be performed in robust conditions. The major drawback of this technique is, however, its inherently weak signal. This has been overcome by the use of methods such as RRS, SERS, TERS, and SRS. Tremendous amount of research activity is currently in progress in these areas of activity. The reviews in Chapter 5 by Kumar et al. and in Chapter 6 by Umapathy et al. highlight the recent activities in areas of IR and Raman spectroscopy and microscopy and their applications. Coherent optical spectroscopy and microscopy and their applications are given in Chapter 5, which provides a detailed account of the principles and instrumentation of the various linear and nonlinear spectroscopy/microscopy techniques. Under the linear spectroscopy/microscopy, the chapter provides an advanced review of the IR (absorption) spectroscopy, confocal microscopy, laser-induced fluorescence spectroscopy/microscopy, and spontaneous Raman spectroscopy/microscopy techniques and illustrates their applications with examples. The nonlinear techniques include a wide range of current topics under coherent Raman spectroscopy (CRS)/microscopy such as CARS, SRS, Raman-induced Kerr effect spectroscopy, balanced-detection Raman-induced Kerr effect spectroscopy, second- and third-harmonic generation spectroscopy/microscopy, and two-photon excitation microscopy. Advantages of nonlinear microscopy over the linear microscopy have been explained. Linear microscopy techniques are either too weak to perform high-speed imaging or they require confocal geometry to get 3D sectioning, whereas nonlinear techniques provide inherent 3D sectioning and are coherent in nature. In all of CRS techniques, the atomic/molecular Raman response is enhanced by many orders of magnitude to go till video-rate imaging speed with chemical specificity. Chapter 6 provides a detailed description of IR and Raman microspectroscopy instrumentation and discusses recent techniques that hold the promise for depth-sensitive Raman applications such as spatially offset Raman spectroscopy (SORS) and universal multiple angle Raman spectroscopy (UMARS) for subsurface analysis and 3D Raman imaging. Because UMARS works on the principle of collection of Raman signal from multiple angles (4π collection) and at all planes, one can easily collect Raman signals from samples hidden within other strongly scattering materials using either conventional lenses or optical fibers. The use of this technique for noninvasive and nondestructive detection of hazardous chemicals packed in containers and also deep imaging of tissues, such as the breast cancer tissues, has been described. Several applications of microspectroscopic techniques to the study of materials and biology, such as spectroscopic studies of dyes and explosives using nanoparticle–carbon composites, study of biochemical changes in different kinds of biological samples (cells, tissues, bacteria, biofluids), rapid analysis of highly absorbing samples or samples in aqueous environments by ATR-IR microspectroscopy, and to the study of art and archaeology have been discussed.

2.5. Resonance Raman Spectroscopy

Advancements in instrumentation, with major emphasis on the source and detectors, and the analytical potential of RRS have been reviewed in Chapter 7 by Chowdury. Ti-Sa (titanium–sapphire) lasers capable of emitting ultrashort pulses (between a few picoseconds and 10  femtoseconds), having a complete wavelength tunability in the red and NIR (650–1100  nm) regions, and the modern optics augmented with confocal microscopes and sensitive charge-coupled device (CCD) detector systems with high signal-to-noise ratio have provided a promising platform for the real-world analytical applications of RRS in agriculture and life sciences; in art, archaeology, and forensics; and in detecting and understanding the photochemical behavior of explosives. These and some more recent applications of RRS in carbon nanotube research, in isomerization dynamics of organic molecules, and in understanding the contributions of different electronic states of aromatic closed-ring compounds to Raman scattering are highlighted. Recent studies on the applications of RRS to understand the excited electronic states of metal–ligand complexes and charge transfer mechanism in halide-substituted hybrid perovskite solar cells are also discussed.

2.6. Two-Photon Absorption Spectroscopy

The advent of optical parametric amplifiers and ultrafast lasers (with pulses of the order of femtoseconds) has accelerated growth in research activities related to the fundamental and applied aspects of 2PA, which is a third-order process, several orders of magnitude weaker than linear absorption at low light intensities. Because of its remarkable features, such as the advantageous excitation in the NIR region and the high spatial localization of excitation, 2PA spectroscopy has found increasing applications for the study of materials having large nonlinear cross sections. Among the different types of materials investigated in the last decade by 2PA, organic materials have an advantage over the other types of materials mainly as their optical properties can easily be modified or optimized by using molecular engineering methods. In Chapter 8, Mendonça et al. have reviewed developments in the theoretical and experimental aspects of this field and described the potential of the 2PA spectroscopy to investigate organic materials. Combined use of the experimental techniques based on absorption and fluorescence mechanisms and the two-photon theory has been described with several examples for obtaining information about promising molecular designs in organic molecules that may improve the nonlinear optical response and decrease the irradiance threshold necessary to generate a specific optical effect. Organic chromophores with high 2PA cross section can be obtained by producing a linear combination of dipolar molecules, the so-called branched molecules. This molecular design has a cumulative effect on the nonlinear optical features, such that the 2PA cross section considerably increases with the number of branches. In this regard, dendrimers, which are organic molecules containing a highly branched molecular structure, are discussed. Strategies for 20-fold enhancement in 2PA cross section and for getting spectrally tuned 2PA cross sections through the use of supramolecular assembly and octupolar arrangements have been described. The chapter also focuses on 2PA spectroscopy with polarization control and describes its potential for identifying the nature of the excited states and molecular structure of randomly oriented chromophores, a feature that can be exploited for the development of photonics devices. It also presents an overview of the two-photon circular dichroism (2PACD) and its use for getting information about the magnitude of electric quadrupole moment and conformational and electronic properties of molecules.

2.7. Femtosecond Raman Spectroscopy

Since most of the natural processes in atoms and molecules occur on very fast timescales in the range of picoseconds (10−¹²  s) to femtoseconds (10−¹⁵  s), pico and subpico vibrational spectroscopies are well suited for the study of excited electronic states, radical reactions, electron transfer, and vibrational dynamics. In Chapter 9, Dasgupta and coworkers have presented femtosecond stimulated Raman spectroscopy (FSRS) as the preferred spectroscopic tool to look at transient structural changes in the molecular structure. The authors have given theoretical construction of FSRS as a four-wave mixing process and have discussed in detail the necessary optical layout and instrumentation for its successful laboratory execution. To get a more reliable and background-free spectrum, different variants of the FSRS technique such as femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), in-line interferometric FSRS (IIFSRS), and wavelength-modulated FSRS have been discussed.

A number of examples have been used to highlight the utility of FSRS in solving challenging problems in chemistry. These range from mechanism of photoisomerization in small molecular systems such as azobenzenes to solving the reaction coordinates in photoreaction in biological molecules such as rhodopsin. Examples such as excited-State dynamics in conjugated polymers, isomerization reactions in signaling proteins, proton transfer–mediated emission in GFP (green fluorescent protein), and ultrafast ring cyclization reaction have been used to demonstrate the utility of FSRS in understanding complex reaction mechanisms in chemistry and biology.

2.8. Two-Dimensional Correlation Spectroscopy

2DCOS and its applications have been discussed by Jung et al. in Chapter 10. The chapter introduces the basic concept of generalized 2DCOS and its new and noteworthy developments, such as chemometrics-combined 2DCOS, moving-window 2D analysis, orthogonal sample design and related techniques, projection 2D analysis, and 2D codistribution spectroscopy (2DCDS). These are illustrated with examples. The chapter presents an exhaustive review covering 280 articles of the various applications of 2DCOS in vibrational and optical spectroscopy of materials and samples such as polymers, proteins, and peptides; nanomaterials and composites; pharmaceuticals and medicals; DNA; nucleic acid; food science; natural materials; and environmental science. It also discusses 2D heterospectral correlation analysis (comprising of heterospectral correlation, heteroperturbation (or hybrid) correlation, and heterosample correlation), using which the correlation between different spectral signals under the same perturbation (thermal, electrical, chemical, etc.) can be detected. 2D heterospectral analysis provides correlation not only between closely related spectroscopic measurements, such as IR and Raman spectra, but also between completely different types of spectroscopic or physical techniques, such as IR and X-ray spectroscopy. The chapter reports numerous studies on temperature-induced spectral changes of polymers. It uses the example of 2D IR and 2D X-ray photoelectron (XPS) correlation spectra of spin-coated films of biodegradable poly(3-hydroxy butyrate-co-3-hydroxyhexanoate) to reveal the existence of two crystalline components, namely the well-ordered primary crystals and less ordered secondary crystals, on the basis of the temperature-dependent IR and XPS spectra.

2.9. Laser Spectroscopy of Nanomaterials

In Chapter 11, Dwivedi has reviewed the recent advancements in the fast developing field of spectroscopic studies of nonmaterials that possess quite different and interesting luminescent properties than the bulk materials. The optical properties of the nonmaterials may also be manipulated by controlling the degrees of freedom of electron propagation by creating various nanostructures. Some of the techniques to characterize nonmaterials and the nanostructures, such as laser-induced fluorescence, time-resolved spectroscopy, femtosecond time-resolved microscopy, and ultrashort pump–probe spectroscopy, have been discussed with suitable examples, and the unconventional lasing action in nanomaterials, the random lasing, has been analyzed. The chapter also discusses the potential of ultrashort pump–probe spectroscopy to get in-depth understanding of cooling and thermalization rates of hot carriers, the lifetimes of phonons, the formation time of excitons, screening of optical–phonon–carrier interactions, dynamics of the ballistic transport, mechanism of laser annealing, etc.

2.10. Laser-Induced Breakdown Spectroscopy

Being a relatively noninvasive technique requiring only a nanogram or a picogram of material, much interest has recently been shown by researchers in LIBS over traditional methods of atomic spectroscopy as an advanced analytical tool to identify and quantify different elements in ores, alloys, soils, aqueous solutions, oil, water, aerosols, and many other liquid samples. Besides its traditional use in areas of environmental monitoring, forensic investigations involving energetic and explosive materials, space exploration, and biomedical research, etc., more recently, LIBS has found applications in the elemental analysis of plant materials and in food science to identify and quantify the nutrients in food products to understand about the quality of food. While focusing on applications to food science, a thorough review of the advancements in the theory, instrumentation, and experimental techniques of LIBS for solid and liquid samples and applications in diverse areas has been provided in Chapter 12 by Singh et al.

2.11. Photoacoustic Spectroscopy

Recent developments in PAS, a research area based on detection of acoustic waves resulting from nonradiative transitions in atoms and molecules in different physical states, have been reviewed in Chapter 13 by Thakur. Though started in the 19th century, PAS waited for almost a century till the invention of a strong light source in the form of lasers before it could find its true potential and important place as an analytical and diagnostic technique. With the advent of tunable lasers, particularly the QCLs in the mid-infrared region, this spectroscopic technique has found more and more field-based applications in industry, health care, and environment, including security environment, while it continues to reveal newer aspects of molecular structure and molecular dynamics. Because of its ability to perform studies of opaque or highly diffusive materials, PAS has become a very widely used technique in the biomedical field. The chapter describes the theory of radiative and nonradiative transitions in molecules and production of photoacoustic (PA) signal in gases and solids. It also provides a detailed account of the experimental techniques and setups in PAS such as designing of PA cells for static and flowing gaseous and for solid samples, quartz tuning fork piezoelectric transducers for PA detection etc. Several examples, such as PA detection of harmful chemicals and gas molecules (aerosols, ethylene, methanol, ozone etc.), gases emanating from human body such as CO, ammonia, etc., and dangerous drugs and explosives, have been used to illustrate the application of PAS. The chapter also describes PA imaging, a hybrid technique making use of optical absorption and ultrasonic wave propagation, which can provide high-resolution structural, functional, and molecular images of cells, tissues, and organs in vivo. Its more recent development, combined PAT and OCT (optical coherence tomography) imaging, makes it possible to visualize vascular anatomy and tissue micromorphology. The applications of the two imaging techniques have been illustrated through examples.

2.12. Matrix Isolation Spectroscopy

The electronic structure and chemical properties of reactive molecular compounds and intermediates are heavily influenced by the environment (e.g., solvation and aggregation), especially if they are open-shell species. The matrix isolation (MI) technique offers the possibility to study the electronic structure and intrinsic properties of these species, free of such extrinsic influences. First introduced in 1954 by Pimentel and coworkers, MI is used as a means of trapping and characterization of reactive species, such as free radicals, ions, and other unstable or transient species, in inert host media such as Ar, Ne, Kr, Xe, and N2, typically in the ratio 1:1000 at 5–20  K. The inert medium allows for an extended lifetime of the reactive species. The first spectroscopic studies were carried out in the IR region as this experimental technique offers advantages of sharp spectral linewidths and removal of spectral congestion, thereby leading to simple, highly resolved spectral features. It was followed by MI Raman spectroscopy. MI studies are also being conducted using visible, UV,