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An Introduction
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Laser Spectroscopy and Laser Imaging
An Introduction

Helmut H. Telle
Instituto Pluridisciplinar - Universidad Complutense de Madrid
Madrid, Spain
Ángel González Ureña
Instituto Pluridisciplinar - Universidad Complutense de Madrid
Madrid, Spain
CRC Press
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© 2018 by Taylor & Francis Group, LLC

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International Standard Book Number-13: 978-1-4665-8822-6 (Hardback)

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 v

Contents

Series Preface xxi

Preface xxiii

Acknowledgments xxv

Authors xxvii

Chapter 1 Introduction 1

Chapter 2 Interaction of Light with Matter 9

Chapter 3 The Basics of Lasers 29

Chapter 4 Laser Sources Based on Gaseous, Liquid,

or Solid-State Active Media 69

Chapter 5 Laser Sources Based on Semiconductor Media

and Nonlinear Optic Phenomena 99
vi Contents

Chapter 6 Common Spectroscopic and Imaging

Detection Techniques 129

Chapter 7 Absorption Spectroscopy and Its Implementation 163

Chapter 8 Selected Applications of Absorption

Spectroscopy 193

Chapter 9 Fluorescence Spectroscopy

and Its Implementation 229

Chapter 10 Selected Applications of Laser-Induced

Fluorescence Spectroscopy 247

Chapter 11 Raman Spectroscopy and Its Implementation 267

Chapter 12 Linear Raman Spectroscopy 295

Chapter 13 Enhancement Techniques

in Raman Spectroscopy 333

Chapter 14 Nonlinear Raman Spectroscopy 365

Chapter 15 Laser-Induced Breakdown Spectroscopy 405

Chapter 16 Laser Ionization Techniques 427

Chapter 17 Basic Concepts of Laser Imaging 469

Chapter 18 Laser-Induced Fluorescence Imaging 499

Chapter 19 Raman Imaging and Microscopy 529

 Contents vii

Chapter 20 Diffuse Optical Imaging 563

Chapter 21 Imaging Based on Absorption and Ion Detection

Methods 597

Bibliography 639

Index 693
http://taylorandfrancis.com
 ix

Detailed Contents

2.1.2 Quantitative description of light

Series Preface xxi absorption—The Beer–Lambert law 12
Preface xxiii
2.2 FLUORESCENCE AND PHOSPHORESCENCE 14
Acknowledgments xxv
Authors xxvii 2.3 LIGHT SCATTERING 16
2.3.1 Rayleigh scattering 16
Chapter 1 2.3.2 Mie scattering 18
Introduction 1 2.3.3 Reflection and refraction 20
2.4 LIGHT SCATTERING: INELASTIC PROCESSES 22
1.1 LASERS AND THEIR IMPACT ON
2.4.1 Brillouin scattering 22
SPECTROSCOPY AND IMAGING 2
2.4.2 Raman scattering 23
1.1.1 Laser properties of importance
to spectroscopy 3 2.5 BREAKTHROUGHS AND THE CUTTING
1.1.2 Concepts of laser spectroscopy EDGE 25
and imaging 4 2.5.1 Breakthrough: Color in prehistoric
times 26
1.2 ORGANIZATION OF THE BOOK 4 2.5.2 At the cutting edge:
1.2.1 Introduction to photon–matter Single-photon spectroscopy
interaction processes, laser sources, of a single molecule 26
and detection methodologies 4
1.2.2 Spectroscopic techniques Chapter 3
and their applications 5 The Basics of Lasers 29
1.2.3 Laser-spectroscopic imaging 7
3.1 FRAMEWORK FOR LASER ACTION 30
Chapter 2 3.1.1 Rate equations 30
Interaction of Light with Matter 9 3.1.2 Population inversion in the
steady-state limit 32
2.1 ABSORPTION AND EMISSION 3.1.3 Laser cavities 33
OF RADIATION 9 3.1.4 Laser gain 34
2.1.1 Einstein coefficients and transition 3.1.5 Cavity dynamics and the evolution
probabilities 10 of laser photons 35
x Detailed Contents

3.2 LASER CAVITIES: SPATIAL FIELD Chapter 4

DISTRIBUTIONS AND LASER BEAMS 38 Laser Sources Based on Gaseous,
3.2.1 Transverse mode structure 38
Liquid, or Solid-State Active Media 69
3.2.2 Gaussian beams and their
propagation 40 4.1 PARAMETERS OF IMPORTANCE FOR
LASER SPECTROSCOPY AND LASER
3.3 LASER CAVITIES: MODE FREQUENCIES,
IMAGING 70
LINE SHAPES, AND SPECTRA 43
3.3.1 Frequency mode structure 43 4.2 GAS LASER SOURCES (MOSTLY FIXED
3.3.2 Line profiles and widths 45 FREQUENCY) 72
3.3.3 Laser linewidth, gain bandwidth,
and laser spectrum 47 4.3 DYE LASERS (TUNABLE FREQUENCY) 74
3.3.4 Single-mode laser operation 49 4.4 SOLID-STATE LASER SOURCES
3.4 LASER CAVITIES: TEMPORAL (FIXED AND TUNABLE FREQUENCY) 78
CHARACTERISTICS 50 4.4.1 Nd:YAG lasers 78
3.4.1 CW operation and laser 4.4.2 Ti:sapphire lasers 80
output modulation 50 4.5 FIBER LASER SOURCES 84
3.4.2 Pulsed laser operation 52 4.5.1 Wavelength selection
3.4.3 Mode locking: Generation and tunability 87
of ultrashort picosecond 4.5.2 Q-Switched and mode-locked
and femtosecond pulses 55 pulse generation 90
3.4.4 Group delay dispersion: 4.5.3 Supercontinuum sources 92
Shortening and lengthening 4.5.4 Fiber lasers versus bulk
ultrashort (chirped) pulses 60 solid-state lasers 94
3.5 POLARIZATION AND COHERENCE 4.6 BREAKTHROUGHS AND THE CUTTING
PROPERTIES OF LASERS AND EDGE 95
LASER BEAMS 61 4.6.1 Breakthrough: Ti:sapphire lasers 95
3.5.1 Laser polarization 61 4.6.2 At the cutting edge: OFCs for
3.5.2 Tailoring the polarization of high-resolution spectroscopy 96
a laser beam: Linear, circular,
and radial polarization 62 Chapter 5
3.5.3 Coherence 64 Laser Sources Based
3.6 BREAKTHROUGHS AND THE CUTTING on Semiconductor Media
EDGE 66 and Nonlinear Optic Phenomena 99
3.6.1 Breakthrough: Theoretical
5.1 SEMICONDUCTOR LASER SOURCES 100
description of modes in a
5.1.1 Principles of laser diodes 101
laser cavity 66
5.1.2 Laser diode resonators 102
3.6.2 At the cutting edge: Steady-state
5.1.3 Monolithic diode laser devices 104
ab initio laser theory for complex
5.1.4 External cavity diode lasers (ECDL) 106
gain media 66
5.1.5 Optically pumped ECDLs 108
 Detailed Contents xi

5.2 QUANTUM CASCADE LASERS 110 6.1.2 Image information and its
retrieval from photon events 133
5.3 LASER SOURCES BASED ON NLO: 6.1.3 Spectral/image information
SUM AND DIFFERENCE FREQUENCY and its retrieval from
CONVERSION 113 charged-particle events 134
5.3.1 Basic principles of frequency
conversion in nonlinear media 113 6.2 PHOTON DETECTION: SINGLE ELEMENT
5.3.2 Phase matching 114 DEVICES 136
5.3.3 Selected nonlinear crystals 6.2.1 PDs and their principal modes
and their common uses 115 of operation 136
5.3.4 Conversion efficiency and ways 6.2.2 Types of PDs 137
to increase it 116 6.2.3 Important operating parameters
5.3.5 Outside- and inside-cavity of PDs 140
NLO-crystal configurations 117 6.2.4 Photomultiplier tubes 141
6.2.5 Important operating parameters
5.4 LASER SOURCES BASED ON NLO: of photomultipliers 142
OPTICAL PARAMETRIC AMPLIFICATION
(DOWN-CONVERSION) 117 6.3 PHOTON DETECTION: MULTIELEMENT
5.4.1 OPG and OPOs 118 ARRAY DEVICES 143
6.3.1 PDA sensors 144
5.5 REMARKS ON LASER SAFETY 121 6.3.2 CCD and CMOS array sensors 144
5.5.1 How do laser wavelengths 6.3.3 On-chip amplified image sensors:
affect our eyes? 121 EMCCD and e-APD devices 147
5.5.2 Maximum permissible 6.3.4 Externally amplified and gated
exposure and accessible image sensors: ICCD devices 148
emission limit 122
5.5.3 Laser classification 124 6.4 CHARGED PARTICLE DETECTION 149
5.5.4 Laser safety eyewear 124 6.4.1 Direct charge detectors—
Faraday cup 150
5.6 BREAKTHROUGHS AND THE CUTTING 6.4.2 Single-element amplifying
EDGE 126 detectors—Channeltron 150
5.6.1 Breakthrough: Semiconductor 6.4.3 Multiple-element amplifying
laser diodes 126 detectors—MCP 150
5.6.2 Breakthrough: Widely tunable
QCLs 127 6.5 DETECTION BY INDIRECT PHENOMENA 151
5.6.3 At the cutting edge: HHG 6.5.1 Photothermal/photoacoustic
and attosecond pulses 127 spectroscopy 152
6.5.2 Photoacoustic imaging 153
Chapter 6 6.5.3 Photoacoustic Raman (stimulated
Common Spectroscopic and Imaging Raman) scattering 154
Detection Techniques 129 6.6 SIGNALS, NOISE, AND SIGNAL RECOVERY
6.1 SPECTRAL AND IMAGE INFORMATION: METHODOLOGIES 154
HOW TO RECOVER THEM FROM 6.6.1 Signals and noise 154
EXPERIMENTAL DATA 129 6.6.2 Low-intensity “continuous”
6.1.1 Spectral information and its signals—Lock-in methods 157
retrieval from photon events 130 6.6.3 Low-intensity pulsed
signals—Gating methods 158
xii Detailed Contents

6.7 BREAKTHROUGHS AND THE CUTTING 7.5 KEY PARAMETERS AND EXPERIMENTAL
EDGE 159 METHODOLOGIES IN ABSORPTION
6.7.1 Breakthrough: First SPECTROSCOPY 183
transistorized lock-in amplifier 160 7.5.1 Wavelength regimes 183
6.7.2 Breakthrough: First 7.5.2 Spectral resolving power 185
demonstration of CCD imaging 160 7.5.3 Experimental methodologies 185
6.7.3 At the cutting edge: Nanoscale 7.6 BREAKTHROUGHS AND THE CUTTING
light detectors and imaging EDGE 191
devices 160 7.6.1 Breakthrough: Absorption
spectroscopy utilizing SC sources 191
Chapter 7 7.6.2 At the cutting edge: Precision laser
spectroscopy of hydrogen:
Absorption Spectroscopy
Challenging QED? 191
and Its Implementation 163
Chapter 8
7.1 CONCEPTS OF LINEAR ABSORPTION
SPECTROSCOPY 163 Selected Applications of Absorption
7.1.1 Absorption coefficient Spectroscopy 193
and cross section 163 8.1 BASIC METHODOLOGIES BASED
7.1.2 Spectral line profiles 164 ON BROADBAND SOURCES 194
8.1.1 BB-AS utilizing SC sources 195
7.2 LINE BROADENING AND LINE SHAPES 8.1.2 Minimum detectable
IN ABSORPTION SPECTROSCOPY 164 concentrations and LODs 196
7.2.1 Natural broadening 165
7.2.2 Collisional or pressure broadening 165 8.2 ABSORPTION SPECTROSCOPY
7.2.3 Doppler broadening 167 USING FREQUENCY COMBS 197
7.2.4 Combined line profiles— 8.2.1 Basic concepts of frequency
The Voigt convolution profile 168 combs 198
7.2.5 Other effects impacting 8.2.2 Measuring and controlling
on linewidth 169 frequency-comb parameters 199
8.2.3 Spectroscopic metrology based
7.3 NONLINEAR ABSORPTION on frequency combs 200
SPECTROSCOPY 170 8.2.4 Direct frequency comb
7.3.1 Saturation spectroscopy 171 spectroscopy—DFCS 201
7.3.2 Polarization spectroscopy 177 8.3 ABSORPTION SPECTROSCOPY USING
TUNABLE DIODE AND QUANTUM-
7.4 MULTIPHOTON ABSORPTION PROCESSES 178 CASCADE LASER (QCL) SOURCES 205
7.4.1 Two-photon absorption 8.3.1 Tunable diode laser absorption
spectroscopy 178 spectroscopy 206
7.4.2 Doppler-free TPA 179 8.3.2 QCL in absorption spectroscopy 210
7.4.3 Multiphoton absorption 8.3.3 cw-QCL absorption spectroscopy 210
and molecular dissociation 180 8.3.4 EC-QCL absorption spectroscopy 211
8.3.5 p-QCL absorption spectroscopy 212
 Detailed Contents xiii

8.4 CAVITY-ENHANCEMENT TECHNIQUES 213 9.4 QUENCHING, TRANSFER, AND DELAY

8.4.1 Intracavity laser absorption OF FLUORESCENCE 237
spectroscopy 213 9.4.1 Fluorescence quenching
8.4.2 Cavity ring-down spectroscopy 214 and the Stern–Volmer law 237
9.4.2 Förster resonance energy
8.5 TERAHERTZ SPECTROSCOPY 216 transfer 238
8.5.1 Basic features and experimental 9.4.3 Delayed fluorescence 240
methodologies 216
8.5.2 Applications of terahertz 9.5 FLUORESCENCE POLARIZATION
spectroscopy in molecular AND ANISOTROPY 240
structure and chemical
analysis 219 9.6 SINGLE-MOLECULE FLUORESCENCE 242
8.5.3 Applications of terahertz 9.7 BREAKTHROUGHS AND THE CUTTING
spectroscopy in biology EDGE 244
and medicine 220 9.7.1 Breakthrough: Coining the term
8.6 PHOTOACOUSTIC AND PHOTOTHERMAL “fluorescence” 244
SPECTROSCOPY WITH LASERS 222 9.7.2 Breakthroughs: First LIF
8.6.1 Quartz-enhanced PAS 224 spectroscopy 244
9.7.3 At the cutting edge: Laser-
8.7 BREAKTHROUGHS AND THE CUTTING stimulated fluorescence on the
EDGE 225 macroscopic level—
8.7.1 Breakthrough: Cavity-enhanced Fluorescing fossils 245
absorption spectroscopy
utilizing SC sources 225 Chapter 10
8.7.2 At the cutting edge: CRDS Selected Applications of Laser-
of optically trapped Induced Fluorescence Spectroscopy 247
aerosol particles 226
10.1 LIF MEASUREMENT INSTRUMENTATION
IN SPECTROFLUORIMETRY 247
Chapter 9
10.2 STEADY-STATE LASER-INDUCED
Fluorescence Spectroscopy
FLUORESCENCE SPECTROSCOPY 249
and Its Implementation 229 10.2.1 LIF in gas-phase molecular
9.1 FUNDAMENTAL ASPECTS spectroscopy 250
OF FLUORESCENCE EMISSION 230 10.2.2 LIF applied to reaction dynamics 250
9.1.1 The concept of fluorophores 230 10.2.3 LIF in analytical chemistry 253
9.1.2 Principal processes in excited- 10.2.4 LIF for medical diagnosis 254
state fluorescence 231 10.3 TIME-RESOLVED LIF SPECTROSCOPY 255
9.2 STRUCTURE OF FLUORESCENCE SPECTRA 233 10.3.1 Measurements of lifetimes
in the FD 256
9.3 RADIATIVE LIFETIMES AND QUANTUM 10.3.2 Measurements of lifetimes
YIELDS 234 in the time domain: TCSPC 257
10.3.3 LIF applied to femtosecond
transition-state spectroscopy 259
xiv Detailed Contents

10.4 LIF SPECTROSCOPY AT THE 11.3.5 Wavelength separation/selection

SMALL SCALE 260 devices 281
10.4.1 LIF microscopy 261 11.3.6 Photon detectors 282
10.4.2 Fluorescence-correlation 11.3.7 Signal acquisition and data
spectroscopy 262 analysis equipment 283

10.5 BREAKTHROUGHS AND THE CUTTING 11.4 RAMAN SPECTROSCOPY

EDGE 264 AND ITS VARIANTS 283
10.5.1 Breakthrough: First LIF 11.4.1 Spontaneous Raman
measurements to resolve the spectroscopy variants 283
internal state distribution 11.4.2 “Enhanced” Raman techniques 284
of reaction products 264 11.4.3 Nonlinear Raman techniques 286
10.5.2 At the cutting edge: FRET 11.5 ADVANTAGES AND DRAWBACKS, AND
measurements of gaseous COMPARISON TO OTHER “VIBRATIONAL”
ionized proteins 265 ANALYSIS TECHNIQUES 288
11.5.1 The problem of fluorescence 289
Chapter 11 11.5.2 Advantages and drawbacks
of Raman spectroscopy, and
Raman Spectroscopy
comparison to (IR) absorption
and Its Implementation 267 spectroscopy 290
11.1 FUNDAMENTALS OF THE RAMAN 11.6 BREAKTHROUGHS AND THE CUTTING
PROCESS: EXCITATION AND DETECTION 268 EDGE 292
11.2 THE STRUCTURE OF RAMAN SPECTRA 271 11.6.1 Breakthrough: UV Raman
11.2.1 Stokes and anti-Stokes Raman spectroscopy 292
scattering 273 11.6.2 At the cutting edge: Atomic
11.2.2 “Pure” rotational Raman spectra 273 properties probed by Raman
11.2.3 Ro-vibrational Raman bands 274 spectroscopy 293
11.2.4 Hot bands, overtones, and
Chapter 12
combination bands 275
11.2.5 Peculiarities in the Raman spectra Linear Raman Spectroscopy 295
from liquids and solid samples 276 12.1 THE FRAMEWORK FOR QUALITATIVE
11.2.6 Polarization effects in Raman AND QUANTITATIVE RAMAN
spectra 277 SPECTROSCOPY 297
12.1.1 Determining and calibrating
11.3 BASIC EXPERIMENTAL the Raman excitation laser
IMPLEMENTATIONS: KEY ISSUES wavelength 298
ON EXCITATION AND DETECTION 277 12.1.2 Calibrating the spectrometer
11.3.1 Laser excitation sources 278 wavelength and Raman
11.3.2 Delivery of excitation laser shift scales 299
light 279 12.1.3 Intensity calibration for
11.3.3 Samples and their incorporation quantitative Raman spectra 300
into the overall setup 280 12.1.4 Quantification of molecular
11.3.4 Raman light collection 280 constituents in a sample 303
 Detailed Contents xv

12.2 MEASURING MOLECULAR PROPERTIES 12.6.2 At the cutting edge: Raman

USING LINEAR RAMAN SPECTROSCOPY 304 spectroscopy in the search
12.2.1 Raman scattering of polarized for life on Mars 331
light waves 305
12.2.2 Depolarization ratios 307 Chapter 13
12.2.3 Measuring depolarization ratio 310 Enhancement Techniques in Raman
12.2.4 Raman optical activity 312 Spectroscopy 333
12.3 RAMAN SPECTROSCOPY OF GASEOUS 13.1 WAVEGUIDE-ENHANCED RAMAN
SAMPLES 314 SPECTROSCOPY 334
12.3.1 Spectroscopy of rotational 13.1.1 Raman spectroscopy using
and vibrational features 315 liquid-core waveguides (LC-OF) 336
12.3.2 Analytical Raman spectroscopy 13.1.2 Hollow-core metal-lined
and process monitoring 317 waveguides 339
12.3.3 Remote sensing using Raman 13.1.3 Hollow-core photonic-crystal
spectroscopy—The Raman fibers 342
LIDAR 318 13.1.4 Measures to reduce fluorescence
12.4 RAMAN SPECTROSCOPY OF LIQUID contributions in backward
SAMPLES 320 Raman setups 345
12.4.1 Spectroscopic aspects of Raman 13.2 CAVITY-ENHANCED RAMAN
spectroscopy in liquids 321 SPECTROSCOPY 347
12.4.2 Analytical aspects of Raman
spectroscopy in liquids 322 13.3 RESONANCE RAMAN SPECTROSCOPY 352
12.4.3 “Super-resolution” Raman 13.3.1 Basic concepts of resonance
spectroscopy 324 Raman scattering 352
13.3.2 Applications of RRS to probing
12.5 RAMAN SPECTROSCOPY OF SOLID of excited electronic state
SAMPLES 326 quantum levels 355
12.5.1 Spectroscopic and structural 13.3.3 Applications of RRS to obtain
information for “ordered” structural information for large
materials 327 molecules 357
12.5.2 Analytical and diagnostic 13.3.4 Applications of RRS to analytical
applications for “soft tissue” problems 358
samples 328
13.4 BREAKTHROUGHS AND THE CUTTING
12.6 BREAKTHROUGHS AND THE CUTTING EDGE 361
EDGE 330 13.4.1 Breakthrough: First RRS
12.6.1 Breakthrough: Raman of heme-proteins 361
spectroscopy in the terahertz 13.4.2 At the cutting edge: Low-
range 330 concentration gas sensors
based on HC-PCFs 362
xvi Detailed Contents

Chapter 14 14.6 COHERENT ANTI-STOKES RAMAN

Nonlinear Raman Spectroscopy 365 SCATTERING AND SPECTROSCOPY: CARS 391
14.6.1 Basic framework for CARS 393
14.1 BASIC CONCEPTS AND CLASSIFICATION 14.6.2 Tuned single-mode
OF NONLINEAR RAMAN RESPONSES 367 and ns-pulse CARS 396
14.1.1 Incoherent vs. coherent signal 14.6.3 Broadband fs-pulse CARS
character 367 and time-resolved CARS 398
14.1.2 Spontaneous vs. stimulated 14.6.4 Spontaneous, stimulated,
scattering processes 368 and coherent anti-Stokes Raman
14.1.3 Homodyne vs. heterodyne spectroscopies in comparison 401
detection 369
14.7 BREAKTHROUGHS AND THE CUTTING
14.2 NONLINEAR INTERACTION EDGE 401
WITH SURFACES: SERS 369 14.7.1 Breakthrough: SERS using
14.2.1 Trying to understand silver films over nanospheres
SERS spectra 370 (AgFON) 401
14.2.2 Single spherical nanoparticle 14.7.2 Breakthrough: Toward
model for SERS 372 “pen-on-paper” SERS substrates 403
14.2.3 E4-enhancement in the Raman 14.7.3 At the cutting edge: Seeing
response 373 a single molecule vibrate
14.2.4 Wavelength dependence of the utilizing tr-CARS 403
E4-enhancement 374
14.2.5 Distance dependence of the Chapter 15
E4-enhancement 374 Laser-Induced Breakdown
14.2.6 Chemical enhancement in the Spectroscopy 405
Raman response 375
14.2.7 SERS substrates 376 15.1 METHOD OF LIBS 405
15.1.1 Basic concepts: Plasma
14.3 VARIANTS OF SERS—TOWARD generation and characterization 406
ULTRALOW CONCENTRATION AND 15.1.2 Basic experimental setups
ULTRAHIGH SPATIAL RESOLUTION RS 377 and ranging approaches 410
14.3.1 Preconcentration of ultralow 15.1.3 Double-pulse excitation 410
concentration samples— 15.1.4 Portable, remote, and standoff
SLIPSERS 377 LIBS 411
14.3.2 Single-molecule SERS 379 15.1.5 Femtosecond LIBS 413
14.3.3 Principles of tip-enhanced RS 382
15.2 QUALITATIVE AND QUANTITATIVE
14.4 HYPER-RAMAN SPECTROSCOPY: HRS 384 LIBS ANALYSES 413
14.5 STIMULATED RAMAN SCATTERING 15.3 SELECTED LIBS APPLICATIONS 417
AND SPECTROSCOPY: SRS 386 15.3.1 Application of LIBS to liquids
14.5.1 SRS using tunable probe laser and samples submerged
sources 387 in liquids 417
14.5.2 SRS using ps- and fs-laser 15.3.2 Detection of hazardous
sources (fs-SRS) 388 substances by ST-LIBS 420
 Detailed Contents xvii

15.3.3 Space applications 421 16.4 ZEKE SPECTROSCOPY 452

15.3.4 Industrial applications 423 16.4.1 Methodology of ZEKE
spectroscopy 453
15.4 BREAKTHROUGHS AND THE CUTTING 16.4.2 Measurement modality of
EDGE 425 pulsed-field ionization: PFI-ZEKE 454
15.4.1 Breakthrough: Quantitative 16.4.3 Examples of high-resolution
LIBS analysis using nanosecond- ZEKE spectroscopy 456
and femtosecond-pulse lasers 425 16.4.4 MATI spectroscopy 460
15.4.2 At the cutting edge: Elemental
chemical mapping of biological 16.5 TECHNIQUE OF H ATOM RYDBERG
samples using LIBS 426 TAGGING 462
16.5.1 Reaction H + D2 ! HD + D 463
Chapter 16 16.5.2 Reaction of F atoms with
Laser Ionization Techniques 427 H2 molecules: Dynamical
resonances 464
16.1 BASIC CONCEPTS OF REMPI 427 16.5.3 Four-atom reaction
16.1.1 Quantitative description OH + D2 ! HOD + D 464
of REMPI in the framework
of rate equations 429 16.6 BREAKTHROUGHS AND THE CUTTING
16.1.2 REMPI signal intensity 430 EDGE 465
16.1.3 Selection rules for the ionization 16.6.1 Breakthrough: First state-
step in REMPI 433 resolved REMPI spectrum
16.1.4 Conceptual experimental REMPI of a molecule 465
setups 435 16.6.2 At the cutting edge: Ultrahigh
sensitivity PAH analysis
16.2 APPLICATIONS OF REMPI IN MOLECULAR using GC-APLI-MS 466
SPECTROSCOPY AND TO CHEMICAL
INTERACTION PROCESSES 436 Chapter 17
16.2.1 Molecular spectroscopy
Basic Concepts of Laser Imaging 469
utilizing REMPI 436
16.2.2 Investigation of chemical 17.1 CONCEPTS OF IMAGING WITH
reactions utilizing REMPI 440 LASER LIGHT 470
16.2.3 Photodissociation studies 17.1.1 Laser illumination concepts:
utilizing REMPI 444 Point, line, and sheet patterns
16.2.4 REMPI spectroscopy of catalytic in transparent gas and liquid
reactions 445 samples 471
17.1.2 Laser illumination concepts:
16.3 REMPI AND ANALYTICAL CHEMISTRY 446
Point, line, and sheet patterns
16.3.1 REMPI spectroscopy with
in condensed-phase samples 472
isotopologue and isomeric
17.1.3 Image sensing and recording
selectivity 447
concepts 473
16.3.2 REMPI spectroscopy in trace
17.1.4 Multispectral and hyperspectral
and environmental analyses 448
recording 476
16.3.3 Following biological processes
by using REMPI spectroscopy 450
xviii Detailed Contents

17.2 IMAGE GENERATION, IMAGE SAMPLING, 18.2 FLUORESCENCE MOLECULAR

AND IMAGE RECONSTRUCTION 478 TOMOGRAPHY 508
17.2.1 Sampling and its relation 18.2.1 Basic concepts 508
to signal digitization 479 18.2.2 Examples of FMT 509
17.2.2 Sampling and its relation
to spatial resolution 480 18.3 SUPERRESOLUTION MICROSCOPY 511
17.2.3 Sampling and its relation 18.3.1 STED microscopy 513
to spectral resolution 484 18.3.2 RESOLFT microscopy 515
17.2.4 Image reconstruction 485 18.3.3 SIM and SSIM 516

17.3 SUPERRESOLUTION IMAGING 487 18.4 SUPERRESOLUTION FLUORESCENCE

17.3.1 Sub-Abbé limit localization MICROSCOPY BASED ON
and “classical” superresolution SINGLE-MOLECULE IMAGING 518
strategies 488 18.4.1 Basic principles
17.3.2 Imaging and reconstruction of STORM/PALM 520
strategies for structured 18.4.2 Fluorophore localization 521
illumination methods 490 18.4.3 Factors affecting the resolution
17.3.3 Imaging and reconstruction in STORM/PALM imaging 523
strategies for local-saturation 18.4.4 Toward 3D superresolution
methods 492 imaging: Interferometric PALM 524
17.3.4 Imaging and reconstruction 18.5 BREAKTHROUGHS AND THE CUTTING
strategies for single-molecule EDGE 525
response methods 493 18.5.1 Breakthrough: GFP as a marker
17.4 BREAKTHROUGHS AND THE CUTTING for gene expression 525
EDGE 495 18.5.2 At the cutting edge: Nanometer
17.4.1 Breakthrough: Airy-scan resolution imaging 526
detection in confocal laser
Chapter 19
microscopy 495
17.4.2 At the cutting edge: Single-pixel Raman Imaging and Microscopy 529
detector multispectral imaging 496 19.1 RAMAN MICROSCOPIC IMAGING 529
19.1.1 Concepts of Raman imaging
Chapter 18 and microscopy 530
Laser-Induced Fluorescence Imaging 499 19.1.2 Confocal Raman imaging 531
19.1.3 Hyperspectral Raman imaging
18.1 TWO- AND THREE-DIMENSIONAL
in two dimensions and three
PLANAR LASER-INDUCED
dimensions 533
FLUORESCENCE IMAGING 500
19.1.4 Examples of Raman imaging
18.1.1 PLIF iImaging in gaseous
in biology and medicine 537
samples 500
19.1.5 Nonbiological applications
18.1.2 Selected examples for PLIF
of Raman imaging 539
of gaseous samples 502
18.1.3 PLIF imaging of biological
tissues 506
 Detailed Contents xix

19.2 SURFACE- AND TIP-ENHANCED 20.2.3 Experimental methodology 2:

(SERS AND TERS) RAMAN IMAGING 540 FD systems 572
19.2.1 Biomedical imaging based 20.2.4 Experimental methodology 3:
on SERS 540 TD systems 573
19.2.2 Raman imaging at the 20.2.5 Comparison between
nanoscale: TERS imaging 543 the three experimental
methods 574
19.3 SRL (STIMULATED RAMAN
LOSS) IMAGING 548 20.3 MODELING OF DIFFUSE SCATTERING
19.3.1 Concepts of SRL imaging 548 AND IMAGE RECONSTRUCTION 574
19.3.2 Selected applications 20.3.1 Modeling light transport
of SRL imaging 551 through tissue 574
20.3.2 The forward problem 577
19.4 CARS IMAGING 554 20.3.3 The reverse problem—Principles
19.4.1 Concepts of CARS imaging 554 of image reconstruction 578
19.4.2 Selected applications of CARS
microscopic imaging 557 20.4 CLINICAL APPLICATIONS OF DOI
AND SPECTROSCOPY 581
19.5 BREAKTHROUGHS AND THE CUTTING 20.4.1 DOT and spectroscopy of breast
EDGE 560 cancer 582
19.5.1 Breakthrough: Hyperspectral 20.4.2 Diffuse optical topography
CARS imaging utilizing and tomography of the brain 585
frequency combs 561
19.5.2 At the cutting edge: 20.5 NONCLINICAL APPLICATIONS OF DOI
Superresolution Raman AND SPECTROSCOPY 586
microscopy 561 20.5.1 Single-point bulk measurements
on fruits 587
Chapter 20 20.5.2 Multipoint measurements
Diffuse Optical Imaging 563 on fruits yielding 2D images 588
20.5.3 MSI and HSI of fruits 589
20.1 BASIC CONCEPTS 563
20.1.1 Scattering and absorption 20.6 BRIEF COMPARISON WITH OTHER
in biological tissue 563 MEDICAL IMAGING TECHNIQUES 590
20.1.2 What can we learn from
20.7 BREAKTHROUGHS AND THE CUTTING
diffuse optical imaging
EDGE 593
and spectroscopy? 564
20.7.1 Breakthrough: DOI of brain
20.1.3 Historical snapshots in the
activities 593
development of DOI 566
20.7.2 At the cutting edge:
20.2 BASIC IMPLEMENTATION AND Photoacoustic tomography—
EXPERIMENTAL METHODOLOGIES 566 Toward DOI with high spatial
20.2.1 Key equipment components resolution 594
for DOI 567
20.2.2 Experimental methodology 1:
CW systems 571
xx Detailed Contents

Chapter 21 21.3.5 Measuring time and position:

Imaging Based on Absorption Direct 3D ion imaging 623
21.3.6 Product-pair correlation by ion
and Ion Detection Methods 597
imaging 625
21.1 IMAGING EXPLOITING ABSORPTION
21.4 CHARGED PARTICLE IMAGING:
SPECTROSCOPY: FROM THE MACRO-
SELECTED EXAMPLES FOR ION
TO THE NANOSCALE 597
AND ELECTRON IMAGING 626
21.1.1 Experimental implementation
21.4.1 Photodissociation
of imaging exploiting
with oriented molecules 626
absorption spectroscopy 598
21.4.2 Imaging of the pair-correlated
21.1.2 IR/NIR chemical imaging 600
fragment channels in
21.1.3 Detecting “hidden” structures
photodissociation 628
using terahertz imaging 601
21.4.3 Nonreactive scattering:
21.1.4 IR Imaging at the nanoscale 604
Energy transfer in bimolecular
21.2 IMAGING EXPLOITING ABSORPTION collisions 629
SPECTROSCOPY: SELECTED 21.4.4 Reactive scattering: Bimolecular
APPLICATIONS IN BIOLOGY reactions 631
AND MEDICINE 607 21.4.5 Product-pair correlation
21.2.1 Imaging based on FTIR in bimolecular reactions 632
methodologies 607 21.4.6 Imaging the motion
21.2.2 Imaging based on terahertz of electrons across
methodologies 609 semiconductor heterojunctions 634
21.2.3 Imaging based on
21.5 BREAKTHROUGHS AND THE CUTTING
photoacoustic methodologies 612
EDGE 636
21.3 CHARGED PARTICLE IMAGING: BASIC 21.5.1 Breakthrough: First ion
CONCEPTS AND IMPLEMENTATION 615 imaging experiment 636
21.3.1 Basic concepts of unimolecular 21.5.2 At the cutting edge: PAM—
and bimolecular collisions 616 toward label-free superresolution
21.3.2 Newton sphere 618 imaging 637
21.3.3 Basic experimental setups 619
21.3.4 Methods for improving the Bibliography 639
resolution in ion imaging 620 Index 693
 xxi

Series Preface

T his textbook series offers pedagogical resources for the physical sciences. It
publishes high-quality, high-impact texts to improve understanding of fun-
damental and cutting-edge topics, as well as to facilitate instruction. The authors
are encouraged to incorporate numerous problems and worked examples, as well
as making available solutions manuals for undergraduate- and graduate-level
course adoptions. The format makes these texts useful as professional self-study
and refresher guides as well. Subject areas covered in this series include con-
densed matter physics, quantum sciences, atomic, molecular, and plasma physics,
energy science, nanoscience, spectroscopy, mathematical physics, geophysics,
environmental physics, and so on, in terms of both theory and experiment.
New books in the series are commissioned by invitation. Authors are also
welcome to contact the publisher (Lou M. Han, Executive Editor: lou.han@
taylorandfrancis.com) to discuss new title ideas.
http://taylorandfrancis.com
 xxiii

Preface

S cientific and real-life applications of spectroscopy and imaging, which use

a laser in one form or another, are abundant and a plethora of books have
been written about particular, individual methodologies. To a lesser degree have
general overviews been given, and if so these have been published many years, if
not decades, ago.
In this book, we cover as wide a range of laser spectroscopic and imaging
techniques as possible, and we tried to put these into perspective of use in the
laboratory and in mainstream, real-world applications. While we attempted to be
as inclusive as feasible, we are almost certain that we may have missed one or the
other technique or application. But the book was never meant to be an ency-
clopedia. Rather, we intended to provide the reader with an overview of widely
used techniques, including (1) their basic concepts; (2) an overview of the
underlying theory and common experimental setups; (3) a handful of repre-
sentative key applications that highlight the advantages and caveats of partic-
ular techniques; and (4) a comparison of the merits of certain implementations
with those of other techniques. We end each chapter with brief snapshots of key
events in the evolution of the technique, and cutting-edge developments. Of
course, because of the necessary brevity, their selection is probably rather sub-
jective, and in particular what is judged to be cutting-edge today may become
routine tomorrow.
Overall, the text has been written—as far as possible—at a level suitable for
advanced students and researchers in all fields of science, without delving into
the depths of the underlying theoretical framework, but at the same time pro-
viding sufficiently detailed formulas for the reader to gauge the usefulness of a
particular technique for his or her specific application.

Helmut H. Telle
Ángel González Ureña
Madrid
http://taylorandfrancis.com
 xxv

Acknowledgments

W e take this opportunity to acknowledge the support of many of our friends,

students, postdocs, and colleagues; their efforts in reading through pages
of the manuscript are gratefully recognized. They all provided invaluable input
to improve the text, by pointing out where we went astray or by suggesting
scientific aspects we had overlooked or forgotten.

In particular, we are indebted to our Executive Editor, Lou M. Han, for his
guidance in polishing the layout and content of the book; but also for his skills in
prodding us when we slacked, in giving encouragement when we were down,
and—foremost—in being extremely patient when once again we did not keep to
our schedule in reaching a promised milestone.

Last but not least, without the goodwill of our families, who supported us through
long night hours and weekends, we might have thrown in the towel well before
finishing this book; our gratitude and appreciation goes to them.
http://taylorandfrancis.com
 xxvii

Authors

T he authors have known each other well for more than 30 years; they love
and share many research interests in fundamental and applied physics and
chemistry, all involving lasers in one form or another.
Helmut H. Telle earned his degrees in physics from the
University of Cologne, Germany, in 1972 (BSc), 1974
(MSc), and 1979 (PhD), respectively. He exploited his
newly gained experience in and passion for laser spec-
troscopy during an extensive postdoctoral research period,
which found him expanding his horizons at universi-
ties and research institutions in Canada and France, at
physics and chemistry departments. In 1984, he settled
in Wales, United Kingdom, to embrace a career in teach-
ing and research in laser physics at Swansea University.
His research activities—both at Swansea and within the
framework of numerous international collaborations—encompass a wide range
of laser-spectroscopic techniques. He used these predominantly for trace detec-
tion of atomic and molecular species, and applied them to analytical problems
in industry, biomedicine, and the environment on the one hand, but also to
various fundamental aspects in science on the other hand. After nearly 30 years
in Wales, he relocated to Spain to join the Instituto Pluridisciplinar of Madrid’s
Universidad Complutense. Here he pursues new frontiers in laser spectroscopy
of exotic species of interest to astroparticle physics and astronomy.

Ángel González Ureña graduated in chemistry from the

University of Granada (Spain) in 1968, and then earned his
PhD in physical chemistry at the Universidad Complu-
tense de Madrid in 1972. During the period 1972–1974,
he carried out postdoctoral research at the Universities
of Madison (Wisconsin, USA) and Austin (Texas, USA),
embracing reaction dynamics in molecular beams. On his
return to Spain, he took up the position of associate pro-
fessor in chemical physics at the Universidad Complutense
de Madrid, and was promoted to full professor in 1983.
xxviii Authors

The focus of his research activities was mainly on gas-phase, cluster, and surface
reaction dynamics, mostly utilizing molecular beam and laser spectroscopic
techniques. In said work, he was one of the pioneers in measuring threshold
energies in chemical reactivity when changing the translational and electronic
energy of the reactants. In recent years, his interests branched out into the appli-
cation of laser technologies to analytical chemistry, environmental chemistry,
biology, and food science. He is heading the Department of Molecular Beams and
Lasers at the Instituto Pluridisciplinar, associated with Madrid’s Universidad
Complutense; for the first 10 years of the institute’s existence, he also was its first
director. In 2016 he received the Richard B. Bernstein Medal for “… lifetime
achievements in the field of chemical stereo-dynamics.”
Another random document with
no related content on Scribd:
behind, a horse was dragging, with a long rope, a small, deeply
laden canal-boat, not pretty like this one, which went swiftly and
merrily along by steam. But at last it came to a stand, in front of two
huge wooden gates which shut the canal in, and through every
crevice of which the pent-in water kept spouting in tiny cataracts.
“That’s the first of the locks,” said papa, who had seen it all before,
and took his little girl to the end of the boat to show her the wonderful
sight.
She was not old enough to have it explained, or to understand what
a fine piece of engineering work this canal is. It cuts across country
from sea to sea, and the land not being level, but rising higher in the
middle, and as you know water will not run up a hillside and down
again, these locks had to be made. They are, so to speak, boxes of
water with double gates at either end. The boat is let into them, and
shut in; then the water upon which it floats is gradually raised or
lowered according as may be necessary, until it reaches the level of
the canal beyond the second gate, which is opened and the boat
goes in. There are eight or nine of these locks within a single mile,—
a very long mile, which occupies fully an hour. So the captain told his
passengers they might get out and walk, which many of them did.
But Sunshine, her papa and mamma, were much more amused in
watching the great gates opening and shutting, and the boat rising or
falling through the deep sides of the locks. Besides, the little girl
called it “a bath,” and expressed a strong desire to jump in and
“swim like a fish,” with mamma swimming after her! So mamma
thought it as well to hold her fast by her clothes the whole time.
Especially when another interest came,—three or four little Highland
girls running alongside, jabbering gayly, and holding out glasses of
milk. Her own bottle being nearly drained, Sunny begged for some;
and the extraordinary difficulty papa had in stretching over to get the
milk without spilling it, and return the empty glass without breaking it,
was a piece of fun more delightful than even the refreshing draught.
“Again!” she said, and wanted the performance all repeated for her
private amusement.
She had now resumed her old tyranny over her papa, whom she
pursued everywhere. He could not find a single corner of the boat in
which to hide and read his newspaper quietly, without hearing the
cry, “Where’s my papa? Sunny must go after papa,” and there was
the little figure clutching at his legs. “Take her up in your arms! up in
your own arms!” To which the victim, not unwillingly, consented, and
carried her everywhere.
Little Sunshine’s next great diversion was dinner. It did not happen
till late in the afternoon, when she had gone through, cheerfully as
ever, another change of boat, and was steaming away through the
open sea, which, however, was fortunately calm as a duck-pond, or
what would have become of this little person?
Papa questioned very much whether she was not far too little a
person to dine at the cabin-table with all the other grown-up
passengers, but mamma answered for her that she would behave
properly,—she always did whenever she promised. For Sunny has
the strongest sense of keeping a promise. Her one argument when
wanting a thing, an argument she knows never denied, is, “Mamma,
you promised.” And her shoemaker, who once neglected to send
home her boots, has been immortalised in her memory as “Mr.
James So-and-so, who broke his promise.”
So, having promised to be good, she gravely took her papa’s hand
and walked with him down the long cabin to her place at the table.
There she sat, quite quiet, and very proud of her position. She ate
little, being too deeply occupied in observing everything around her.
And she talked still less, only whispering mysteriously to her mamma
once or twice.
“Sunny would like a potato, with butter on it.” “Might Sunny have one
little biscuit—just one?”
But she troubled nobody, spilt nothing, not even her glass of water,
though it was so big that with both her fat hands she could scarcely
hold it; and said “Thank you” politely to a gentleman who handed her
a piece of bread. In short, she did keep her promise, conducting
herself throughout the meal with perfect decorum. But when it was
over, I think she was rather glad.
“Sunny may get down now?” she whispered; adding, “Sunny was
quite good, she was.” For the little woman always likes to have her
virtues acknowledged.
And in remounting the companion-ladder, rather a trial for her small
legs, she looked at the steward, who was taking his money, and
observed to him, in a confidential tone, “Sunny has had a good
dinner; Sunny liked it,”—at which the young man couldn’t help
laughing.
But everybody laughs at Sunny, or with her,—she has such an
endless fund of enjoyment in everything. The world to her is one
perpetual kaleidoscope of ever changing delights.
Immediately after dinner she had a pleasure quite new. Playing
about the deck, she suddenly stopped and listened.
“Mamma, hark! there’s music. May Sunny go after the music?” And
her little feet began to dance rather than walk, as, pulling her
mamma by the hand, she “went after” a German band that was
playing at the other end of the vessel.
Little Sunshine had never before heard a band, and this was of wind
instruments, played very well, as most German musicians can play.
The music seemed to quiver all through her, down to her very toes.
And when the dance-tune stopped, and her dancing feet likewise,
and the band struck up the beautiful “Wacht am Rhein,”—the “Watch
on the Rhine,”—(oh! if its singers had only stopped there, defending
their fatherland, and not invaded the lands of other people!), this little
girl, who knew nothing about French and Prussians, stood absorbed
in solemn delight. Her hands were folded together (a trick she has),
her face grew grave, and a soul far deeper than three years old
looked out of her intent eyes. For when Sunny is earnest, she is very
earnest; and when she turns furious, half a dozen tragedies seem
written in her firm-set mouth, knitted brow, and flashing eyes.
She was disposed to be furious for a minute, when her Lizzie tried to
get her away from the music. But her mamma let her stay, so she did
stay close to the musicians, until the playing was all done.
It was growing late in the afternoon, near her usual bedtime, but no
going to bed was possible. The steamboat kept ploughing on
through lonely seas, dotted with many islands, larger or smaller, with
high mountains on every side, some of them sloping down almost to
the water’s edge. Here and there was a solitary cottage or
farmhouse, but nothing like a town or village. The steamboat
seemed to have the whole world to itself,—sea, sky, mountains,—a
magnificent range of mountains! behind which the sun set in such
splendour that papa and mamma, watching it together, quite forgot
for the time being the little person who was not old enough to care
for sunsets.
When they looked up, catching the sound of her laughter, there she
was, in a state of the highest enjoyment, having made friends, all of
her own accord, with two gentlemen on board, who played with her
and petted her extremely. One of them had just taken out of his
pocket a wonderful bird, which jumped out of a box, shook itself,
warbled a most beautiful tune, and then popped down in the box
again; not exactly a toy for a child, as only about half a dozen have
ever been made, and they generally cost about a hundred guineas
apiece.
Of course Sunny was delighted. She listened intently to the warble,
and whenever the bird popped down and hid itself again, she gave a
scream of ecstasy. But she cannot enjoy things alone.
“May mamma come and see it? Mamma would like to see it, she
would!” And, running back, Sunny drew her mamma, with all her little
might, over to where the gentlemen were sitting.
They were very polite to the unknown lady, and went over the
performance once again for her benefit. And they were exceedingly
kind to her little girl, showing a patience quite wonderful, unless,
indeed, they had little girls of their own. They tried pertinaciously to
find out Sunny’s name, but she as persistently refused to disclose it,
—that is, anything more than her Christian name, which is rather a
peculiar one, and which she always gives with great dignity and
accuracy, at full length. (Which, should they really have little girls of
their own, and should they buy this book for them and read it, those
two gentlemen will probably remember; nor think the worse of
themselves that their kindness helped to while away what might
otherwise have been rather dreary, the last hour of the voyage,—a
very long voyage for such a small traveller.)
It was ended at last. The appointed pier, a solitary place where only
one other passenger was landed, stood out distinct in the last rays of
sunset. Once again the child was carried across one of those shaky
gangways,—neither frightened nor cross and quite cheerful and wide
awake still. Nay, she even stopped at the pier-head, her attention
caught by some creatures more weary than herself.
Half a dozen forlorn sheep, their legs tied together, and their heads
rolling about, with the most piteous expression in their open eyes, lay
together, waiting to be put on board. The child went up to them and
stroked their faces.
“Poor little baa-lambs, don’t be so frightened; you won’t be
frightened, now Sunny has patted you,” said she, in her tenderest
voice. And then, after having walked a few yards:
“Sunny must go back. Please, mamma, may Sunny go back to say
good-bye to those poor little baa-lambs?”
But the baa-lambs had already been tossed on board, and the
steamer was away with them into the dark.
Into the dark poor little Sunny had also to go; a drive of nine miles
across country, through dusky glens, and coming out by loch sides,
and under the shadow of great mountains, above whose tops the
stars were shining. Only the stars, for there was no moon, and no
lamps to the carriage; and the driver, when spoken to, explained—in
slow Highland English, and in a mournful manner, evidently not
understanding the half of what was said to him—that there were
several miles farther to go, and several hills to climb yet; and that the
horse was lame, and the road not as safe as it might be. A prospect
which made the elders of the party not perfectly happy, as may well
be imagined.
But the child was as merry as possible, though it was long past her
tea-time and she had had no tea, and past bedtime, yet there was no
bed to go to; she kept on chattering till it was quite dark, and then
cuddled down, making “a baby” of her mamma’s hand,—a favourite
amusement. And so she lay, the picture of peace, until the carriage
stopped at the welcome door, and there stood a friendly group with
two little boys in front of it. After eleven hours of travelling, Little
Sunshine had reached a shelter at last!
 CHAPTER VI.
Sunrise among the mountains. Who that has ever seen it can forget
it? Sunny’s mamma never could.
Arriving here after dark, she knew no more of the place than the
child did. But the first thing she did on waking next morning was to
creep past the sofa where Sunny lay,—oh, so fast asleep! having
had a good scream overnight, as was natural after all her fatigues,—
steal cautiously to the window, and look out.
Such a sight! At the foot of a green slope, or sort of rough lawn, lay
the little loch so often spoken of, upon which Sunny was to go a-
fishing and catch big salmon with Maurice’s papa. Round it was a
ring of mountains, so high that they seemed to shut out half the sky.
These were reflected in the water, so solidly and with such a sharp,
clear outline, that one could hardly believe it was only a reflection.
Above their summit was one mass of deep rose-colour, and this also
was repeated in the loch, so that you could not tell which was
reddest, the water or the sky. Everything was perfectly still; not a
ripple moved, not a leaf stirred, not a bird was awake. An altogether
new and magic world.
Sunny was too much of a baby yet to care for sunrise, or, indeed, for
anything just now, except a good long sleep, so her mamma let her
sleep her fill; and when she woke at last she was as bright as a bird.
Long before she was dressed, she heard down-stairs the voices of
the five little boys who were to be her companions. Their papa and
mamma having no objection to their names being told, I give them,
for they were five very pretty names: Maurice, Phil, Eddie, Franky,
and Austin Thomas. The latter being the youngest, though by no
means the smallest or thinnest, generally had his name in full, with
variations, such as Austin Tummas, or Austin Tummacks. Maurice,
too, was occasionally called Maurie,—but not often, being the eldest,
you see.
He was seven, very small for his age, but with a face almost angelic
in its delicate beauty. The first time Sunny saw him, a few months
before, she had seemed quite fascinated by it, put her two hands on
his shoulders, and finally held up her mouth to kiss him,—which she
seldom does to any children, rather preferring “grown-ups,” as she
calls them, for playfellows. She had talked ever since of Maurice,
Maurice’s papa, Maurice’s boat, and especially of Maurice’s “little
baby,” the only sister of the five boys. Yet when he came to greet her
this morning, she was quite shy, and would not play with him or
Eddie, or even Franky, who was nearer her own age; and when her
mamma lifted up Austin Thomas, younger than herself but much
bigger in every way, and petted him a little, this poor little woman fell
into great despair.
“Don’t kiss him. I don’t want you to kiss Austin Thomas!” she cried,
and the passion which can rise at times in her merry blue eyes rose
now. She clung to her mamma, almost sobbing.
Of course this was not right, and, as I said before, the little girl is not
a perfect little girl. She is naughty at times, like all of us. Still,
mamma was rather sorry for her. It was difficult for an only child,
accustomed to have her mamma all to herself, to tumble suddenly
into such a crowd of boys, and see that mamma could be kind to and
fond of other children besides her own, as all mothers ought to be,
without taking away one atom from the special mother’s love, which
no little people need be jealous over. Sunny bore the trial pretty well,
on the whole. She did not actually cry,—but she kept fast hold of her
mamma’s gown, and watched her with anxious eyes whenever she
spoke to any other child, and especially to Austin Thomas.
The boys were very kind to her. Maurice went and took hold of her
hand, trying to talk to her in his gentle way; his manners were as
sweet as his face. Eddie, who was stronger and rougher, and more
boyish, wanted her to go down with him to the pier,—a small erection
of stones at the shallow edge of the loch, where two or three boats
always lay moored. Consequently the boys kept tumbling in and out
of them,—and in and out of the water, too, very often,—all day long.
But the worst they ever could get was a good wetting,—except
Austin Thomas, who one day toddled in and slipped down, and,
being very fat, could not pull himself up again; so that, shallow as the
water was, he was very near being drowned. But Maurice and Eddie
were almost “water babies,”—so thoroughly at home in the loch,—
and Eddie, though under six years old, could already handle an oar.
“I can low” (row,—he could not speak plain yet). “I once lowed
grandpapa all across the loch. Shall I low you and the little girl?”
But mamma rather hesitated at accepting the kind offer, and
compromised the matter by going down to the pier with Sunny in her
arms, to watch Eddie “low,”—about three yards out and back again,
—in a carefully moored boat. Sunny immediately wanted to go too,
and mamma promised her she should, after breakfast, when papa
was there to take care of her.
So the little party went back to the raised terrace in front of the
house, where the sun was shining so bright, and where Phil, who
was in delicate health, stood looking on with his pale, quiet face,—
sadly quiet and grave for such a child,—and Franky, who was
reserved and shy, stopped a moment in his solitary playing to notice
the newcomer, but did not offer to go near her. Austin Thomas,
however, kept pulling at her with his stout, chubby arms, but whether
he meant caressing or punching it was difficult to say. Sunny
opposed a dignified resistance, and would not look at Austin Thomas
at all.
“Mamma, I want to stop with you. May Sunny stop with you?”
implored she. “You said Sunny should go in the boat with you.”
Mamma always does what she says, if she possibly can, and,
besides, she felt a sympathy for her lonely child, who had not been
much used to play with other children. So she kept Sunny beside her
till they went down together—papa too—for their first row on the
loch.
Such a splendid day! Warm but fresh—how could it help being fresh
in that pure mountain air, which turned Sunny’s cheeks the colour of
opening rosebuds, and made even papa and mamma feel almost as
young as she? Big people like holidays as well as little people, and it
was long since they had had a holiday. This was the very perfection
of one, when everybody did exactly as they liked; which consisted
chiefly in doing nothing from morning till night.
Sunny was the only person who objected to idleness. She must
always be doing something.
“I want to catch fishes,” said she, after having sat quiet by mamma’s
side in the stern of the boat for about three minutes and a half:
certainly not longer, though it was the first time she had ever been in
a boat in all her life, and the novelty of her position sufficed to sober
her for just that length of time. “I want to catch big salmon all by my
own self.”
A fishing-rod had, just as a matter of ceremony, been put into the
boat; but as papa held the two oars, and mamma the child, it was
handed over to Lizzie, who sat in the bow. However, not a single
trout offering to bite, it was laid aside, and papa’s walking-stick used
instead. This was shorter, more convenient, and had a beautiful
hooked handle, which could catch floating leaves. Leaves were
much more easily caught than fishes, and did quite as well.
 Little Sunshine goes fishing.
The little girl had now her heart’s desire. She was in a boat fishing.
“Sunny has caught a fish! Such a big fish!” cried she, in her shrillest
treble of delight, every time that event happened. And it happened
so often that the bench was soon quite “soppy” with wet leaves.
Then she gave up the rod, and fished with her hands, mamma
holding her as tight as possible, lest she should overbalance, and be
turned into a fish herself. But water will wet; and mamma could not
save her from getting her poor little hands all blue and cold, and her
sleeves soaked through. She did not like this; but what will not we
endure, even at two and three-quarters old, in pursuit of some great
ambition? It was not till her hands were numbed, and her pinafore
dripping, that Sunny desisted from her fishing, and then only
because her attention was caught by something else even more
attractive.
“What’s that, mamma? What’s that?”
“Water-lilies.”
Papa, busily engaged in watching his little girl, had let the boat drift
upon a shoal of them, which covered one part of the loch like a
floating island. They were so beautiful, with their leaves lying like
green plates flat on the surface of the water, and their white flowers
rising up here and there like ornamental cups. No wonder the child
was delighted.
“Sunny wants a water-lily,” said she, catching the word, though she
had never heard it before. “May Sunny have one, two water-lilies?
Two water-lilies! Please, mamma?”
This was more easily promised than performed, for, in spite of papa’s
skill, the boat always managed to glide either too far off, or too close
to, or right on the top of the prettiest flowers; and when snatched at,
they always would dive down under water, causing the boat to lurch
after them in a way particularly unpleasant. At last, out of about a
dozen unsuccessful attempts, papa captured two expanded flowers,
and one bud, all with long stalks. They were laid along the seat of
the boat, which had not capsized, nor had anybody tumbled out of it,
—a thing that mamma considered rather lucky, upon the whole, and
insisted on rowing away out of the region of water-lilies.
“Let us go up the canal, then,” said papa, whom his host had already
taken there, to show him a very curious feature of the loch.
Leading out of one end of it, and communicating between it and a
stream that fed it from the neighbouring glen, was a channel, called
“the canal.” Unlike most Highland streams, it was as still as a canal;
only it was natural, not artificial. Its depth was so great, that a stick
fifteen feet long failed to find the bottom, which, nevertheless, from
the exceeding clearness of the water, could be seen quite plain, with
the fishes swimming about, and the pebbles, stones, or roots of trees
too heavy to float, lying as they had lain, undisturbed, year after year.
The banks, instead of shallowing off, went sheer down, as deep as in
the middle, so that you could paddle close under the trees that
fringed them,—gnarled old oaks, queerly twisted rowans or beeches,
and nut-trees with trunks so thick and branches so wide-spreading,
that the great-great-grandfathers of the glen must have gone nutting
there generations back.
Yet this year they were as full as ever of nuts, the gathering of which
frightened mamma nearly as much as the water-lilies. For papa,
growing quite excited, would stand up in the boat and pluck at the
branches, and would not see that nutting on dry land, and nutting in
a boat over fifteen or twenty feet of water, were two very different
things. Even the little girl, imitating her elders, made wild snatches at
the branches, and it was the greatest relief to mamma’s mind when
Sunny turned her attention to cracking her nuts, which her sharp little
teeth did to perfection.
“Shall I give you one, mamma? Papa, too?” And she administered
them by turns out of her mouth, which, if not the politest, was the
most convenient way. At last she began singing a song to herself,
“Three little nuts all together! three little nuts all together!” Looking
into the little girl’s shut hands, mamma found—what she in all her
long life had never found but once before, and that was many, many
years ago—a triple nut,—a “lucky” nut; as great a rarity as a four-
leaved shamrock.
“Oh, what a prize! will Sunny give it to mamma?” (which she did
immediately). “And mamma will put it carefully by, and keep it for
Sunny till she is grown a big girl.”
“Sunny is a big girl now; Sunny cracks nuts for papa and mamma.”
Nevertheless, mamma kept the triple nut, as she remembered her
own mamma keeping the former one, when she herself was a little
girl. When Sunny grows a woman, she will find both.
Besides nuts, there were here and there along the canal-side long
trailing brambles, with such huge blackberries on them,—
blackberries that seem to take a malicious pleasure in growing
where nobody can get at them. Nobody could gather them except
out of a boat, and then with difficulty. The best of them had, after all,
to be left to the birds.
Oh, what a place this canal must have been for birds in spring! What
safe nests might be built in these overhanging trees! what ceaseless
songs sung there from morning till night! Now, being September,
there were almost none. Dead silence brooded over the sunshiny
crags and the motionless loch. When, far up among the hills, there
was heard the crack of a gun,—Maurice’s papa’s gun, for it could of
course be no other,—the sound, echoed several times over, was
quite startling. What had been shot,—a grouse, a snipe, a wild duck?
Perhaps it was a roe-deer? Papa was all curiosity; but mamma, who
dislikes shooting altogether, either of animals or men, and cannot
endure the sight of a gun, even unloaded, was satisfied with hearing
it at a distance, and counting its harmless echoes from mountain to
mountain.
What mountains they were!—standing in a circle, gray, bare, silent,
with their peaks far up into the sky. Some had been climbed by the
gentlemen in this shooting-lodge or by Donald, the keeper, but it was
hard work, and some had never been climbed at all. The clouds and
mists floated over them, and sometimes, perhaps, a stray grouse, or
capercailzie, or ptarmigan, paid them a visit, but that was all. They
were too steep and bare even for the roe-deer. Yet, oh! how grand
they looked, grand and calm, like great giants, whom nothing small
and earthly could affect at all.
The mountains were too big, as yet, for Little Sunshine. Her baby
eyes did not take them in. She saw them, of course, but she was
evidently much more interested in the nuts overhead, and the fishes
under water. And when the boat reached “The Bower,” she thought it
more amusing still.
“The Bower,” so called, was a curious place, where the canal grew
so narrow, and the trees so big, that the overarching boughs met in
the middle, forming a natural arbour,—only of water, not land,—
under which the boat swept for a good many yards. You had to stoop
your head to avoid being caught by the branches, and the ferns and
moss on either bank grew so close to your hand, that you could
snatch at them as you swept by, which Little Sunshine thought the
greatest fun in the world.
“Mamma, let me do it. Please, let Sunny do it her own self.”
To do a thing “all my own self” is always a great attraction to this
independent little person, and her mamma allows it whenever
possible. Still there are some things which mamma may do, and little
people may not, and this was one of them. It was obliged to be
forbidden as dangerous, and Little Sunshine clouded over almost to
tears. But she never worries her mamma for things, well aware that
“No,” means no, and “Yes,” yes; and that neither are subject to
alteration. And the boat being speedily rowed out of temptation’s way
into the open loch again, she soon found another amusement.
On the loch, besides water-fowl, such as wild ducks, teal, and the
like, lived a colony of geese. They had once been tame geese
belonging to the farm, but they had emigrated, and turned into wild
geese, making their nests wherever they liked, and bringing up their
families in freedom and seclusion. As to catching them like ordinary
geese, it was hopeless; whenever wanted for the table they had to
be shot like game. This catastrophe had not happened lately, and
they swam merrily about,—a flock of nine large, white, lively,
independent birds, which could be seen far off, sailing about like a
fleet of ships on the quiet waters of the loch. They would allow you to
row within a reasonable distance of them, just so close and no
closer, then off they flew in a body, with a great screeching and
flapping of wings,—geese, even wild geese, being rather unwieldy
birds.
Their chief haunt was a tiny island just at the mouth of the canal, and
there papa rowed, just to have a look at them, for one was to be shot
for the Michaelmas dinner. (It never was, by the by, and, for all I
know, still sails cheerfully upon its native loch.)
“Oh, the ducks—the ducks!” (Sunny calls all water-birds ducks.) She
clapped her hands, and away they flew, right over her head, at once
frightening and delighting her; then watched them longingly until they
dropped down again, and settled in the farthest corner of the loch.
“Might Sunny go after them? Might Sunny have a dear little duck to
play with?”
The hopelessness of which desire might have made her turn
melancholy again, only just then appeared, rowing with great energy,
bristling with fishing-rods, and crowded with little people as well as
“grown-ups,” the big boat. It was so busy that it hardly condescended
to notice the little pleasure-boat, with only idle people, sailing about
in the sunshine, and doing nothing more useful than catching water-
lilies and frightening geese.
Still the little boat greeted the large one with an impertinent hail of
“Ship ahoy! what ship’s that?” and took in a cargo of small boys,
who, as it was past one o’clock, were wanted home to the nursery
dinner. And papa rowed the whole lot of them back to the pier, where
everybody was safely landed. Nobody tumbled in, and nobody was
drowned,—which mamma thought, on the whole, was a great deal to
be thankful for.
 CHAPTER VII.
Life at the glen went on every day alike, in the simplest, happiest
fashion, a sort of paradise of children, as in truth it was. Even the
elders lived like children; and big people and little people were
together, more or less, all day long. A thing not at all objectionable
when the children are good children, as these were.
The boys were noisy, of course, and, after the first hour of the
morning, clean faces, hands, and clothes became a difficulty quite
insurmountable, in which their mother had to resign herself to fate;
as the mamma of five boys, running about wild in the Highlands,
necessarily must. But these were good, obedient, gentlemanly little
fellows, and, had it been possible to keep them clean and whole,
which it wasn’t, very pretty little fellows, too.
Of course they had a few boyish propensities, which increased the
difficulty. Maurice, for instance, had an extraordinary love for all
creeping things, and especially worms. On the slightest pretence of
getting bait to fish with, he would go digging for them, and stuff them
into his pockets, whence, if you met him, you were as likely as not to
see one or two crawling out. If you remonstrated, he looked
unhappy, for Maurice really loved his worms. He cherished them
carefully, and did not in the least mind their crawling over his hands,
his dress, or his plate. Only, unfortunately, other people did. When
scolded, he put his pets meekly aside, but always returned to them
with the same love as ever. Perhaps Maurice may turn out a great
naturalist some day.
The one idea of Eddie’s life was boats. He was for ever at the little
pier waiting a chance of a row, and always wanting to “low”
somebody, especially with “two oars,” which he handled
uncommonly well for so small a child. Fortunately for him, though not
for his papa and the salmon-fishers, the weather was dead calm, so
that it was like paddling on a duck-pond; and the loch being shallow
just at the pier, except a few good wettings, which he seemed to
mind as little as if he were a frog, bright, brave, adventurous Eddie
came to no harm.
Nor Franky, who imitated him admiringly whenever he could. But
Franky, who was rather a reserved little man, and given to playing
alone, had, besides the pier, another favourite play-place, a hollow
cut out in the rock to receive the burn which leaped down from the
hillside just behind the house. Being close to the kitchen door, it was
put to all sorts of domestic uses, being generally full of pots and
pans, saucepans and kettles,—not the most advisable playthings,
but Franky found them charming. He also unluckily found out
something else,—that the hollow basin had an outlet, through which
any substance, sent swimming down the swift stream, swam away
beautifully for several yards, and then disappeared underground.
And the other end of this subterraneous channel being in the loch, of
course it disappeared for ever. In this way there vanished
mysteriously all sorts of things,—cups and saucers, toys, pinafores,
hats; which last Franky was discovered in the act of making away
with, watching them floating off with extreme delight. It was no moral
crime, and hardly punishable, but highly inconvenient. Sunny’s
beloved luggie, which had been carried about with her for weeks,
was believed to have disappeared in this way, and, as it could not
sink, is probably now drifting somewhere about on the loch, to the
great perplexity of the fishes.
Little Phil, alas! was too delicate to be mischievous. He crept about
in the sunshine, not playing with anybody, but just looking on at the
rest, with his pale, sweet, pensive face. He was very patient and
good, and he suffered very much. One day, hearing his uncle at
family prayers pray that God would make him better, he said, sadly,
“If He does, I wish He would make haste about it.” Which was the
only complaint gentle, pathetic little Phil was ever heard to utter.
Sunny regarded him with some awe, as “the poor little boy who was
so ill.” For herself, she has never yet known what illness is; but she
is very sympathetic over it in others. Anybody’s being “not well” will
at once make her tender and gentle; as she always was to Phil. He
in his turn was very kind to her, lending her his “music,” which was
the greatest favour he could bestow or she receive.
This “music” was a box of infantile instruments, one for each boy,—
trumpet, drum, fife, etc., making a complete band, which a rash-
minded but affectionate aunt had sent them, and with which they
marched about all day long, to their own great delight and the
corresponding despair of their elders. Phil, who had an ear, would go
away quietly with his “music,”—a trumpet, I think it was,—and play it
all by himself. But the others simply marched about in procession,
each making the biggest noise he could, and watched by Sunny with
admiration and envy. Now and then, out of great benevolence, one
of the boys would lend her his instrument, and nobody did this so
often as Phil, though of them all he liked playing his music the best.
The picture of him sitting on the door-step, with his pale fingers
wandering over his instrument, and his sickly face looking almost
contented as he listened to the sound, will long remain in
everybody’s mind. Sunny never objected to her mamma’s carrying
him, as he often had to be carried; though he was fully six years old.
He was scarcely heavier than the little girl herself. Austin Thomas
would have made two of him.
Austin’s chief peculiarity was this amiable fatness. He tumbled about
like a roly-poly pudding, amusing everybody, and offending no one
but Little Sunshine. But his persistent pursuit of her mamma, whom
he insisted on calling “Danmamma” (grandmamma), and following
whenever he saw her, was more than the little girl could bear, and
she used to knit her brows and look displeased. However, mamma
never took any notice, knowing what a misery to itself and all about it
is a jealous child.
Amidst these various amusements passed the day. It began at 8 a.
m., when Sunshine and her mamma usually appeared on the terrace
in front of the house. They two were “early birds,” and so they got
“the worm,”—that is, a charming preliminary breakfast of milk, bread
and butter, and an egg, which they usually ate on the door-step.
Sometimes the rest, who had had their porridge, the usual breakfast
of Scotch children,—and very nice it is, too,—gathered around for a
share; which it was pleasant to give them, for they waited so quietly,
and were never rough or rude.
Nevertheless, sometimes difficulties arose. The tray being placed on
the gravel, Maurice often sat beside it, and his worms would crawl
out of his pocket and on to the bread and butter. Then Eddie now
and then spilt the milk, and Austin Thomas would fill the salt-cellar
with sand out of the gravel walk, and stir it all up together with the
egg-spoon; a piece of untidiness which Little Sunshine resented
extremely.
She had never grown reconciled to Austin Thomas. In spite of his
burly good-nature, and his broad beaming countenance (which
earned him the nickname of “Cheshire,” from his supposed likeness
to the Cheshire Cat in “Alice’s Adventures”), she refused to play with
him; whenever he appeared, her eye followed him with distrust and
suspicion, and when he said “Danmamma,” she would contradict him
indignantly.
“It isn’t grandmamma, it’s my mamma, my own mamma. Go away,
naughty boy!” If he presumed to touch the said mamma, it was
always, “Take me up in your arms, in your own arms,”—so as to
prevent all possibility of Austin Thomas’s getting there.