Collisional Effects on Molecular Spectra

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Format: Hardcover
Pub. Date: 2008-08-12
Publisher(s): Elsevier Science
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Summary

Gas phase molecular spectroscopy is a powerful tool for obtaining information on the geometry and internal structure of isolated molecules as well as on the interactions that they undergo. It enables the study of fundamental parameters and processes and is also used for the sounding of gas media through optical techniques. It has been facing always renewed challenges, due to the considerable improvement of experimental techniques and the increasing demand for accuracy and scope of remote sensing applications. In practice, the radiating molecule is usually not isolated but diluted in a mixture at significant total pressure. The collisions among the molecules composing the gas can have a large influence on the spectral shape, affecting all wavelength regions through various mechanisms. These must be taken into account for the correct analysis and prediction of the resulting spectra. This book reviews our current experimental and theoretical knowledge and the practical consequences of collisional effects on molecular spectral shapes in neutral gases. General expressions are first given. They are formal of difficult use for practical calculations often but enable discussion of the approximations leading to simplified situations. The first case examined is that of isolated transitions, with the usual pressure broadening and shifting but also refined effects due to speed dependence and collision-induced velocity changes. Collisional line-mixing, which invalidates the notion of isolated transitions and has spectral consequences when lines are closely spaced, is then discussed within the impact approximation. Regions where the contributions of many distant lines overlap, such as troughs between transitions and band wings, are considered next. For a description of these far wings the finite duration of collisions and concomitant breakdown of the impact approximation must be taken into account. Finally, for long paths or elevated pressures, the dipole or polarizability induced by intermolecular interactions can make significant contributions. Specific models for the description of these collision induced absorption and light scattering processes are presented. The above mentioned topics are reviewed and discussed from a threefold point of view: the various models, the available data, and the consequences for applications including heat transfer, remote sensing and optical sounding. The extensive bibliography and discussion of some remaining problems complete the text. . State of the art on the subject . A bibliography of nearly 1000 references . Tools for practical calculations . Consequences for other scientific fields . Numerous illustrative examples . Fulfilling a need since there is no equivalent monograph on the subject

Author Biography

Jean-Michel Hartmann, Directeur de Recherche au CNRS, Laboratoire Inter-universitaire des Systemes Atmospheriques, Universites Paris VII, Paris XII et CNRS, Faculte des Sciences et Technologie, 61 avenue du General de Gaulle, 94010 Creteil Cedex, France Christian Boulet, Professeur des Universites, Laboratoire de PhotoPhysique Moleculaire, Universite Paris XI et CNRS, Campus d'Orsay (batiment 350), 91405 Orsay Cedex, France Daniel Robert, Professeur emerite des Universites, Institut UTINAM, Universite de Franche-Comte et CNRS, UFR Sciences Techniques, 16 route de Gray, 25030 Besancon Cedex, France

Table of Contents

Forewordp. xiii
Acknowledgmentsp. xv
Introductionp. 1
General Equationsp. 9
Introductionp. 9
Dipole Autocorrelation Functionp. 10
General formalismp. 10
The Hamiltonian of the molecular systemp. 13
Toward "Conventional" Impact Theoriesp. 16
General properties of the correlation functionp. 16
The binary collision approximationp. 17
Initial statistical correlationsp. 19
The impact approximationp. 20
Beyond the Impact Approximationp. 23
Effects of the Radiator Translational Motionp. 25
Collision-Induced Spectrap. 28
Conclusionp. 33
Appendices
Spectral and time domain profiles in various spectroscopiesp. 33
Absorption, emission, and dispersionp. 33
Rayleigh and spontaneous Raman scatteringsp. 35
Nonlinear Raman spectroscopiesp. 38
Time-resolved Raman spectroscopiesp. 42
Some criteria for the approximationsp. 44
The large number of perturbersp. 44
The local thermodynamic equilibriump. 45
The binary collisionsp. 47
The (full) impact assumptionp. 49
The impact relaxation matrixp. 50
Analysis through the time dependencep. 50
Analysis through the frequency dependencep. 54
The Liouville spacep. 55
The resolvent approachp. 58
Spectral-shape expressionp. 58
Rotational invariancep. 60
Detailed balancep. 61
Isolated Linesp. 63
Introductionp. 63
Doppler Broadening and Dicke Narrowingp. 73
The Doppler broadeningp. 74
The Dicke narrowingp. 75
Basic Models for Spectral Line Shapesp. 77
The Lorentz profilep. 77
The Dicke profilep. 78
The Voigt profilep. 79
The Galatry profilep. 80
The Nelkin-Ghatak profilep. 81
Correlated profilesp. 83
Characteristics of the basic profilesp. 85
Speed-Dependent Line-Shape Modelsp. 90
Observation of speed-dependent inhomogeneous profilesp. 90
Basic speed-dependent profilesp. 98
The Rautian-Sobelman modelp. 104
The Keilson-Storer memory modelp. 114
AB Initio Approaches of the Line Shapep. 126
The Waldmann-Snider kinetic equationp. 126
The generalized Hess methodp. 128
Collision kernel methodp. 130
Approaches from a simplified Waldmann-Snider equationp. 133
Conclusionp. 139
Appendix
Computational aspectsp. 140
Algorithms for the Voigt and Galatry profilesp. 140
Computation of speed-dependent profilesp. 142
Collisional Line Mixing (Within Clusters of Lines)p. 147
Introductionp. 147
The Spectral Shapep. 154
Approximations and general expressionsp. 154
Asymptotic expansionsp. 158
Computational aspects and recommendationsp. 169
Constructing the Impact Relaxation Matrixp. 173
Simple empirical (classical) approachesp. 174
Statistically based energy gap fitting lawsp. 181
Dynamically based scaling lawsp. 188
Semi-classical modelsp. 199
Quantum modelsp. 211
Determining Line-Mixing Parameters from Experimentsp. 218
Introductionp. 218
Relaxation matrix elementsp. 222
First-order line-coupling coefficientsp. 224
Mixed theoretical model and measured spectra fitting approachesp. 227
Literature Reviewp. 227
Available line-mixing datap. 228
Comparisons between predictions and laboratory measurementsp. 229
Comparisons between predictions and atmospheric measurementsp. 232
Conclusionp. 232
Appendices
Vibrational dephasingp. 233
Perturbed wave functionsp. 237
Resonance broadeningp. 238
The Far Wings (Beyond the Impact Approximation)p. 241
Introductionp. 241
Empirical Modelsp. 243
The x factor approachp. 243
The tabulated continuap. 246
Other approachesp. 248
Far Wings Calculations: The Quasistatic Approachp. 248
General expressionsp. 249
Practical implementation and typical resultsp. 252
The band average line shape: back to the x factorsp. 255
From Resonance to the Far Wing: A Perturbative Treatmentp. 257
General expressionsp. 257
Illustrative resultsp. 259
From Resonance to the Far Wing: A Non-Perturbative Treatmentp. 261
General expressionp. 261
Illustrative resultsp. 263
Conclusionp. 265
Appendix
The water vapor continuump. 266
Definition, properties and semi-empirical modeling of the H[subscript 2]O continuump. 268
On the origin of the water vapor continuap. 269
The self- and N[subscript 2]-broadened continua within the v[subscript 2] bandp. 271
Conclusionp. 272
Collision-Induced Absorption and Light Scatteringp. 275
Introductionp. 275
Collision-Induced Dipoles and Polarizabilities for Diatomic Moleculesp. 276
Collision-Induced Spectra in the Isotropic Approximationp. 277
Two illustrative examples: H[subscript 2] and N[subscript 2]p. 277
Modeling of the line shapep. 281
Effects of the Anisotropy of the Interaction Potentialp. 284
The Importance of Bound and Quasibound States in CIA Spectrap. 290
Interference Between Permanent and Induced Dipoles (CIA) or Polarizabilities (CILS)p. 293
Depolarized light scattering spectra of H[subscript 2] and N[subscript 2]p. 294
The HD problemp. 296
Intercollisional dipsp. 300
Conclusionp. 301
Consequences for Applicationsp. 303
Introductionp. 303
Basic Equationsp. 304
Radiative heat transferp. 304
Remote sensingp. 307
Isolated Linesp. 311
The basic Lorentz and Voigt profilesp. 311
More refined isolated line profilesp. 314
Line Mixing within Clusters of Linesp. 318
Allowed Band Wings and CIAp. 325
Allowed band wingsp. 325
Collision-induced absorptionp. 331
Conclusionp. 333
Toward Future Researchesp. 335
Introductionp. 335
Dicke Narrowing in Speed-Dependent Line-Mixing Profilesp. 335
Models of profiles in the hard collision framep. 335
Experimental tests in multiplet spectrap. 339
From Resonances to the Far Wingsp. 343
Semi-classical approachp. 344
Generalized scaling approachp. 348
Tomorrow's Spectroscopic Databasesp. 348
Isolated linesp. 349
Line mixingp. 351
Far-wings and collision-induced absorptionp. 352
Conclusionp. 354
Appendixp. 357
Abbreviations and Acronymsp. 357
Symbolsp. 360
Units and Conversionsp. 362
Referencesp. 365
Subject Indexp. 409
Table of Contents provided by Ingram. All Rights Reserved.

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