Molecular and Laser Spectroscopy: Advances and Applications: Volume 2

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Molecular and Laser
Spectroscopy:
Advances and Applications: Volume 2
Copyright
Dedication
Contributors
Preface
1-
Introduction and overview
	1 - Introduction
		1.1 - Significance of spectroscopic studies
		1.2 - Spectroscopic techniques
			1.2.1 - Infrared spectroscopy
			1.2.2 - Raman spectroscopy
			1.2.3 - Electronic spectroscopy
			1.2.4 - Other techniques
	2 - Background information and overview
		2.1 - Vibrational optical activity spectroscopy
		2.2 - Cavity ring-down spectroscopy
		2.3 - Terahertz time-domain spectroscopy (THz-TDS)
		2.4 - Matrix isolation studies
		2.5 - Optogalvanic spectroscopy
		2.6 - Far- and deep-ultraviolet spectroscopy for inorganic semiconductor
		2.7 - Hyper-Rayleigh scattering (HRS)
		2.8 - Vibrational sum frequency generation (VSFG) spectroscopy
		2.9 - Surface-enhanced Raman spectroscopy
		2.10 - Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS)
		2.11 - Stimulated Raman scattering (SRS)
		2.12 - Synchrotron-based UV resonance Raman scattering (SR-UVRR)
		2.13 - Stand-off Raman spectroscopy
		2.14 - Ultrafast time-resolved molecular spectroscopy techniques
			2.14.1 - Overview of time-resolved electronic spectroscopic studies
			2.14.2 - Overview of ultrafast time-resolved molecular spectroscopy studies
		2.15 - Infrared and Raman imaging and microscopy in medical applications
			2.15.1 - Overview of infrared imaging and microscopy
			2.15.2 - Overview of Raman imaging and microscopy
	References
2 -
Vibrational optical activity spectroscopy
	Chapter outline
	1 - Introduction
	2 - Principles of vibrational optical activity spectroscopy
		2.1 Raman optical activity
		2.2 - Nonresonance Raman optical activity
		2.3 - Resonance effect in Raman optical activity
		2.4 - Vibrational circular dichroism
	3 - Instrumentation of vibrational optical activity spectroscopy
		3.1 - Instrumentation of Raman optical activity
		3.2 - Instrumentation of vibrational circular dichroism
	4 - Spectral analysis in vibrational optical activity spectroscopy
		4.1 - Quantum chemical calculations of vibrational optical activity spectra
		4.2 - Effects of solvent and conformational averaging
		4.3 - Applications to large systems
	5 - Selected applications of Raman optical activity and vibrational circular dichroism spectroscopy
		5.1 - Raman optical activity
			5.1.1 - Absolute configuration of small molecules
			5.1.2 - Peptides and proteins
			5.1.3 - Carbohydrates
			5.1.4 - Chromophoric proteins
			5.1.5 - Resonance Raman optical activity
		5.2 - Vibrational circular dichroism
			5.2.1 - Determination of absolute configuration
			5.2.2 - Determination of absolute configuration by vibrational circular dichroism exciton coupling
			5.2.3 - Structural analysis of biopolymers
			5.2.4 - Supramolecules
	6 - Summary
	References
3 -
Cavity ring-down spectroscopy: recent technological advances and applications
	Chapter outline
	1 - Introduction
	2 - Principle of CRDS operation
		2.1 - Sensitivity of CRDS
	3 - Mode Structure of an optical cavity
	4 - Brief historical overview
	5 - Continuous wave (cw) cavity ring-down spectroscopy
	6 - Recent technological advances
		6.1 - Rapidly swept cw-CRD spectroscopy
		6.2 - Cavity-enhanced (CE) optical frequency comb (OFC) spectroscopy
		6.3 - Optical feedback (OF) cavity-enhanced spectroscopy
		6.4 - Pound–Drever–Hall (PDH) locking and frequency stabilized (FS) cavity ring-down spectroscopy
		6.5 - Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS)
		6.6 - Frequency-agile, rapid-scanning (FARS) cavity ring-down spectroscopy
		6.7 - Quantum cascade laser (QCL) coupled cavity ring-down spectroscopy
	7 - Applications of cavity ring-down spectroscopy
		7.1 - High-resolution fundamental spectroscopy
		7.2 - Environmental monitoring
		7.3 - Dissolved trace gas monitoring
		7.4 - Bio-medical diagnostics
		7.5 - Plasma diagnostics
		7.6 - Liquid-phase CRDS
	8 - Conclusion and future perspectives
	References
4 -
Terahertz time-domain spectroscopy: advanced techniques
	Chapter outline
	1 - Introduction
	2 - Basic concepts of THz time-domain spectroscopy
		2.1 - Generation and detection of picosecond electromagnetic bursts
			2.1.1 - Photo-conducting antennas
			2.1.2 - Electrooptic (EO) antennas
		2.2 - THz-TDS systems and THz-TDS signals
			2.2.1 - THz-TDS setups
			2.2.2 - THz-TDS signals
			2.2.3 - Noise and errors
		2.3 - Extraction of the THz parameters of samples
			2.3.1 - THz-TDS in transmission
			2.3.2 - THz-TDS in reflection
			2.3.3 - Precision of the extraction
		2.4 - Comparison with other far-infrared characterization techniques
			2.4.1 - CW optoelectronic systems
			2.4.2 - CW VNA systems
			2.4.3 - Comparison with FTIR
	3 - Dedicated measurements
		3.1 - Characterization of thin films
		3.2 - Characterization of liquids
		3.3 - Ellipsometry
		3.4 - Characterization of anisotropic materials and magnetic materials
		3.5 - Characterization of scattering materials
		3.6 - Determination of the sample thickness
	4 - THz-TDS time-resolved studies: from pump-and-probe to THz spectro-chronography techniques
		4.1 - Pump-and-probe THz-TDS
		4.2 - THz spectro-chronography: the windowed Fourier transform procedure
	5 - Generation of THz waves in gases
		5.1 - Generalities and historical overview
		5.2 - Photo-induced ionization of a gas
			5.2.1 - Ponderomotive force
		5.3 - Laser wakefield-accelerated electron bunch transition radiation
		5.4 - Generation in the presence of an electrical bias
		5.5 - THz generation in gases excited by the fundamental and second harmonic frequencies of the laser beam
			5.5.1 - THz generation by four-wave mixing rectification
			5.5.2 - Optical and photocurrent asymmetry at the plasma
		5.6 - Estimation of the THz pulse electric field using air-based photonics
		5.7 - THz-TDS with air-plasma sources
	6 - Conclusion
	References
5 - Spectroscopy of molecules confined in solid para-hydrogen
	Chapter outline
	1 - Introduction
	2 - Properties of H2
		2.1 - Ortho and para species
		2.2 - Properties of solid p-H2
		2.3 - Quantum solid
	3 - Instrumentation: preparation of p-H2 and matrix-isolation spectroscopy
		3.1 - Ortho-to-para converter
		3.2 - Matrix-isolation spectrometry
		3.3 - Ortho-H2 mixing ratio in solid para-H2
		3.4 - Estimation of mixing ratio from IR spectra
		3.5 - Estimation of sample temperature
	4 - Spectroscopy of stable molecules
		4.1 - High-resolution infrared spectroscopy
			4.1.1 - Methane [12,43,44]
			4.1.2 - Propene [46]
		4.2 - Large amplitude motion: methyl internal rotation
		4.3 - Interaction between guest molecules and o-H2 impurity
		4.4 - Electronic spectroscopy
	5 - Spectroscopy of free radicals and ions
		5.1 - Diminished cage effect and spectroscopy of radicals
			5.1.1 - Photolysis in situ
			5.1.2 - Bimolecular reactions: reaction of Cl atom with unsaturated hydrocarbon molecules
		5.2 - Protonated species
			5.2.1 - Infrared spectroscopy of protonated species
			5.2.2 - Electron bombardment during p-H2 matrix deposition
			5.2.3 - Application to polycyclic aromatic hydrocarbons (PAH)
			5.2.4 - Application to small molecules
			5.2.5 - Identification of proton-bound dimers
		5.3 - Hydrogen atoms and hydrogen reaction in solid p-H2
			5.3.1 - Generation of hydrogen atoms in solid p-H2
			5.3.2 - Spectroscopy of hydrogenated species
			5.3.3 - Hydrogen abstraction reaction
	6 - Future perspective
	Acknowledgments
	References
6 - Optogalvanic spectroscopy and its applications
	Chapter outline
	1 - Introduction
	2 - Physics of optogalvanic spectroscopy
	3 - Experimental systems
		3.1 - Laser optogalvanic spectroscopy of dc discharge
		3.2 - Laser optogalvanic spectroscopy with hollow cathode discharge
		3.3 - Laser optogalvanic spectroscopy of radio frequency and microwave discharges
		3.4 - Laser optogalvanic spectroscopy in flames
	4 - Applications of optogalvanic spectroscopy
		4.1 - Optogalvanic spectroscopy of rare gases
		4.2 - Optogalvanic spectroscopy of molecules
		4.3 - Mobility measurements of ions and small particles in flames
		4.4 - Electron-photodetachment studies by optogalvanic spectroscopy
			4.4.1 - Photodetachment threshold
		4.5 - Intracavity optogalvanic spectroscopy
		4.6 - Wavelength calibration
		4.7 - Laser frequency and power stabilization
		4.8 - Rydberg states of atoms
		4.9 - Understanding the physics of OGS
	5 - Conclusion
	Acknowledgments
	References
7 - Far- and deep-ultraviolet spectroscopy for inorganic semiconductor materials
	Chapter outline
	1 - Introduction
	2 - Study of optical properties of TiO2 using radiation spectroscopy and theoretical simulation
	3 - ATR spectroscopy for semiconductor materials
		3.1 - ATR-FUV instrument
		3.2 - ATR-FUV measurements of semiconductor powders
		3.3 - Photon-induced spectral changes of TiO2
	4 - DUV Rayleigh scattering spectroscopy for individual TiO2 nanocrystals
	5 - Applications of UV Raman spectroscopy for semiconductor nanocrystals
		5.1 - Study of TiO2 phase transformation using UV Raman spectroscopy
		5.2 - UV Raman spectroscopy of zirconia nanocrystals
	6 - Summary and future outlook
	References
8 -
First-order hyperpolarizability of organic molecules: hyper-Rayleigh scattering and applications
	Chapter outline
	1 - Introduction
	2 - Microscopic description of the nonlinear optical response: Electronic first-order hyperpolarizability
	3 - Hyper-Rayleigh scattering technique
	4 - Theoretical calculation
		4.1 - Importance of symmetry on the second-order NLO responses
			4.1.1 - Intrinsic symmetry of permutation
			4.1.2 - Kleinman’s symmetry
			4.1.3 - Molecular symmetry
		4.2 - Molecular first-order hyperpolarizability by hyper-Rayleigh scattering experiment
		4.3 - Schemes for the determination of the molecular hyperpolarizabilities
	5 - First-order hyperpolarizability in push-pull octupolar molecules
		5.1 - Enhancing the electronic first-order hyperpolarizability
		5.2 - Comparison between experimental and theoretical data for dynamic first-order hyperpolarizability
		5.3 - Molecular branching effect on the dynamic first-order hyperpolarizability
		5.4 - Quantifying molecular interaction via HRS signal
	6 - Discussing HRS results based on quantum chemical results
	7 - Final Remarks
	Acknowledgments
	References
9 - Heterodyne-detected chiral vibrational sum frequency generation spectroscopy of bulk and interfacial samples
	Chapter outline
	1 - Introduction
	2 - Principles of chiral VSFG spectroscopy
		2.1 - What is VSFG spectroscopy?
		2.2 - VSFG susceptibility and its symmetric properties
		2.3 - VSFG susceptibility and molecular hyperpolarizability
		2.4 - Relation between chiral VSFG susceptibility and the symmetry of Raman tensor
		2.5 - Polarization combinations for chiral and achiral SFG measurements
		2.6 - Modes of SFG signal measurement
			2.6.1 - Narrowband IR scheme and multiplex scheme of SFG spectral measurement
			2.6.2 - Intensity measurement and phase-sensitive measurement of SFG signals
	3 - Experimental setup and the analysis of observed data in HD chiral VSFG
		3.1 - Multiplex HD VSFG spectrometer
		3.2 - Method for analyzing raw data to calculate the susceptibility of a sample
	4 - Applications of HD chiral VSFG spectroscopy
		4.1 - Neat liquid limonene
		4.2 - Vibrationally-electronically doubly-resonant chiral SFG of chiral solutions
		4.3 - Vibrationally-electronically doubly-resonant chiral SFG of chiral monolayers – electronic excitation profiles of comp...
		4.4 - Polymer thin films – bulk-or-interface assignment by polarization dependence
		4.5 - Air/protein solution interfaces
	5 - Concluding remarks
	References
	Appendix A Fresnel factors
10-
Surface-enhanced Raman scattering (SERS) and applications
	Chapter outline
	1 - SERS and its mechanisms: a brief introduction
	2 - SERS-active substrates
		2.1 - Noble metals
		2.2 - Transition metals
		2.3 - Semiconductors
			2.3.1 - Metal oxides
		2.4 - Semiconductor-metal heterostructures
	3 - Mechanism of SERS on semiconductor nanomaterials
		3.1 - Plasmon resonance
		3.2 - Mie resonance
		3.3 - CT resonance
		3.4 - Exciton resonance
		3.5 - Key points of SERS on pure semiconductor nanomaterials
	4 - Applications
		4.1 - Probing CT in dye-sensitized solar cells
			4.1.1 - ZnO-TiO2/N3/Ag
			4.1.2 - Au@Ag/N3/TiO2
		4.2 - Chemical and biological sensing
			4.2.1 - Small ions and toxic molecules
			4.2.2 - Protein biomarkers
			4.2.3 - Cell viability and apoptosis assays
		4.3 - Probing intermolecular interactions
			4.3.1 - The effect of hydrogen bonds on CT
			4.3.2 - Enantioselective discrimination by hydrogen binding
			4.3.3 - ET between redox proteins
	5 - Conclusions and outlook
	References
11- Shell-isolated nanoparticle-enhanced Raman spectroscopy: a review
	1 - Introduction
	2 - Interaction of light with the plasmonic nanoparticles
	3 - Synthesis of plasmonic cores for SHINERS nanoresonators
	4 - Formation of the protecting layer
	5 - Example applications of SHINERS spectroscopy
	6 - Summary
	Acknowledgments
	References
12 - Novel application of stimulated Raman scattering for high-resolution spectroscopic imaging utilizing its phase info...
	Chapter outline
	1 - The brief history and the principle of stimulated Raman scattering microscopy
		1.1 - Principles of spontaneous and coherent Raman scattering
		1.2 - Application of coherent Raman scattering to microscopic imaging
		1.3 - Difficulties in conventional stimulated Raman scattering microscopy and possible solutions
	2 - Interferometric approach for obtaining the phase information from the stimulated Raman scattering signal
		2.1 - Principle of stimulated Raman scattering interferometry
		2.2 - Instrumental setup
		2.3 - Results and discussion
	3 - Differential interference contrast stimulated Raman scattering microscopy
		3.1 - Principle of differential interference contrast–stimulated Raman scattering microscopy
		3.2 - Instrumental setup
		3.3 - Results and discussion
	4 - Near–infrared stimulated Raman scattering photoacoustic spectroscopy
		4.1 - Principle of near–infrared stimulated Raman scattering photoacoustic spectroscopy
		4.2 - Instrumental setup
		4.3 - Results and discussion
	5 - Future plans: introduction of wave-front modulation technique
		5.1 - Improvement of the lateral resolution by spot shaping based on Fourier optics
		5.2 - Acceleration of imaging by multi-focus stimulated Raman scattering microscopy
		5.3 - Image correction by the technique based on adaptive optics
	6 - Conclusion
	Acknowledgments
	References
13 - Synchrotron-based ultraviolet resonance Raman scattering for material science
	Chapter outline
	1 - Introduction to resonance Raman spectroscopy
		1.1 - Light scattering and Raman effect
		1.2 - Resonance Raman scattering
		1.3 - Advantages and limitations of resonance Raman spectroscopy
	2 - Synchrotron-based ultraviolet resonance Raman setup at Elettra
	3 - Ultraviolet resonance Raman for investigation of structure and dynamics of peptides and proteins
		3.1 - Aqueous solvation of peptides
		3.2 - Isotope-labeling for monitoring structural conformations in peptides
		3.3 - Selectivity of synchrotron radiation-based ultraviolet resonance Raman for proteins
	4 - Ultraviolet resonance Raman study of deoxyribonucleic acid and their assemblies
		4.1 - Selectivity of ultraviolet resonance Raman on nucleobases
		4.2 - Conformational stability of deoxyribonucleic acid in aqueous solution
		4.3 - Thermal stability of deoxyribonucleic acid G-quadruplexes complexed with anticancer drug
		4.4 - Complementarity of ultraviolet resonance Raman and infrared spectroscopies for investigation of deoxyribonucleic acid
	5 - Final remarks and perspectives
	References
14 - Concept and applications of standoff Raman spectroscopy techniques
	Chapter outline
	1 - Concept of standoff spectroscopy
	2 - Standoff spectroscopic techniques
		2.1 - Standoff Raman spectroscopy
			2.1.1 - Experimental methods
		2.2 - Time-resolved standoff Raman spectroscopy
		2.3 - Standoff resonance Raman spectroscopy
		2.4 - Standoff spatially offset Raman spectroscopy
		2.5 - Raman–laser-induced breakdown spectroscopy
		2.6 - Raman–light detection and ranging spectroscopy
	3 - Applications
		3.1 - Chemical and mineral detection
		3.2 - Explosives detection
		3.3 - Atmospheric applications
		3.4 - Art and archeology
	4 - Future scope
	References
15 - The role of excited states in deciphering molecules and materials: time-resolved electronic spectroscopic studies
	Chapter outline
	1 - Introduction
	2 - Probing microheterogeneity of a medium by monitoring the spectral properties
		2.1 - Effect of solvent polarity
		2.2 - Photoisomerization
		2.3 - Excited-state proton transfer
	3 - Experimental techniques for monitoring excited-state properties
		3.1 - Time-correlated single-photon counting
			3.1.1 - Time-resolved area normalized emission spectroscopic analysis
		3.2 - Transient absorption spectroscopy
			3.2.1 - Global analysis of transient absorption spectroscopy data
			3.2.2 - A note on time-resolved emission spectra and decay-associated spectra
	4 - Applications
		4.1 - The microenvironment in Nafion probed by ultrafast fluorescence spectroscopy
		4.2 - The effect of protein binding on the dynamics of DNA probed by fluorescence spectroscopy
		4.3 - Early intramolecular events probed by transient absorption spectroscopy
		4.4 - Understanding microenvironment inside thermophilic rhodopsin using transient absorption spectroscopy
		4.5 - Investigating intermolecular charge separation in light-harvesting units using transient absorption spectroscopy
	5 - Conclusion
	References
16 - Ultrafast time-resolved molecular spectroscopy
	Chapter outline
	1 - Introduction
	2 - Transient absorption spectroscopy (flash photolysis)
	3 - Time-resolved fluorescence spectroscopy
		3.1 - Fluorescence lifetime imaging microscopy
		3.2 - Time-resolved fluorescence resonance energy transfer
	4 - Time-resolved linear vibrational spectroscopy
		4.1 - Time-resolved infrared spectroscopy
		4.2 - Time-resolved resonance Raman spectroscopy
	5 - Time-resolved nonlinear vibrational spectroscopy
		5.1 - Time-resolved sum-frequency generation vibrational spectroscopy
			5.1.1 - Steady-state sum-frequency generation vibrational spectroscopy
			5.1.2 - Time-resolved infrared-visible sum-frequency generation vibrational spectroscopy
			5.1.3 - Time-resolved pump/sum-frequency generation-probe spectroscopy
		5.2 - Time-resolved coherent anti-Stokes Raman scattering spectroscopy
		5.3 - Time-resolved femtosecond stimulated Raman spectroscopy
		5.4 - Time-resolved femtosecond Raman-induced Kerr-effect spectroscopy
	6 - Conclusion
	Acknowledgments
	References
17 - Infrared spectroscopic imaging: a case study for digital molecular histopathology
	Chapter outline
	1 - Introduction
	2 - Fundamentals of infrared imaging and considerations for use
		2.1 - Michelson interferometer
		2.2 - Interferogram
		2.3 - Resolution
			2.3.1 - Spectral resolution
			2.3.2 - Spatial resolution
		2.4 - Computational processing
			2.4.1 - Apodization
			2.4.2 - Baseline correction
			2.4.3 - Noise reduction
	3 - Infrared microscope design and influence of optics and sample properties on the data recorded
		3.1 - Imaging setups
		3.2 - Scattering effects
	4 - Applications: a case study of breast cancer
		4.1 - Overview of medical diagnosis
		4.2 - Tumor detection and associated microenvironment
		4.3 - Molecular content in infrared imaging
	5 - Prospects and outlook
	References
18 - Emerging trends in biomedical imaging and disease diagnosis using Raman spectroscopy
	Chapter outline
	1 - Introduction: biomedical Raman spectroscopy
	2 - Biomedical Raman instrumentation: state-of-the-art
		2.1 - Excitation sources
		2.2 - Collection optics and detection system
		2.3 - Integration with microscopes
		2.4 - Fiber optic Raman probes for delivery and collection of light
	3 - Clinical applications of Raman spectroscopy
		3.1 - Ex vivo analysis for disease detection and bioanalyte monitoring
			3.1.1 - Biofluids
			3.1.2 - Bone and mineralized tissues
			3.1.3 - Solid tumors
		3.2 - In vivo tissue analysis for disease detection
			3.2.1 - Intraoperative margin assessment
			3.2.2 - Endoscopic applications
	4 - Preclinical applications beyond disease diagnosis
		4.1 - Insights into metastatic progression of cancer
		4.2 - Personalized cancer therapy and response monitoring
	5 - Cellular analysis using linear and nonlinear Raman imaging
	6 - Surface enhanced Raman spectroscopy
	7 - Concluding remarks
	References
Index
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