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Collisional Effects on
Molecular Spectra
Collisional Effects on
Molecular Spectra
Laboratory Experiments and Models,
Consequences for Applications

Second Edition

JEAN-MICHEL HARTMANN
Directeur de recherche au CNRS, Laboratoire de Météorologie
Dynamique, CNRS et école Polytechnique, Palaiseau, France

CHRISTIAN BOULET
Professeur honoraire des Universités, Institut des Sciences
Moléculaires d'Orsay, CNRS et Université Paris-Saclay, Orsay, France

DANIEL ROBERT
Professeur honoraire des Universités, Institut UTINAM, CNRS et
Université de Franche-Comté, Besançon, France
Elsevier
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Dedication

This book was cowritten by his father

in memory of Yann Robert, to whom his sister Catherine must
now be associated
Contents

Foreword to second edition xiii

Foreword xv
Acknowledgments xvii

I. Introduction 1

II. General equations 11

II.1 Introduction 11
II.2 Dipole autocorrelation function 12
II.2.1 General formalism 12
II.2.2 The Hamiltonian of the molecular system 16
II.3 Toward “conventional” impact theories 18
II.3.1 General properties of the correlation function 19
II.3.2 The binary collision approximation 20
II.3.3 Initial statistical correlations 22
II.3.4 The impact approximation 22
II.4 Beyond the impact approximation 25
II.5 Effects of the radiator translational motion 27
II.6 Collision-induced spectra 31
II.7 Conclusion 36
Appendix II.A Spectral and time domain profiles in various spectroscopies 36
II.A1 Absorption, emission, and dispersion 36
II.A2 Rayleigh and spontaneous Raman scatterings 38
II.A3 Nonlinear Raman spectroscopies 41
II.A4 Time-resolved Raman spectroscopies 45
Appendix II.B Some criteria for the approximations 47
II.B1 The large number of perturbers 47
II.B2 The local thermodynamic equilibrium 48
II.B3 The binary collisions 51
II.B4 The (full) impact assumption 53
Appendix II.C The impact relaxation matrix 54
II.C1 Analysis through the time dependence 54
II.C2 Analysis through the frequency dependence 59
Appendix II.D The Liouville space 60
Appendix II.E The resolvent approach 62
II.E1 Spectral-shape expression 62
II.E2 Rotational invariance 65
II.E3 Detailed balance 66

vii
viii Contents

III. Isolated lines 69

III.1 Introduction 69
III.2 Doppler broadening and Dicke narrowing 81
III.2.1 The Doppler broadening 81
III.2.2 The Dicke narrowing 82
III.3 Basic models for spectral line shapes 84
III.3.1 The Lorentz profile 84
III.3.2 The Dicke profile 86
III.3.3 The Voigt profile 86
III.3.4 The Galatry profile 88
III.3.5 The Nelkin Ghatak profile 89
III.3.6 Correlated profiles 90
III.3.7 Characteristics of the basic profiles 93
III.4 Speed-dependent line-shape models 98
III.4.1 Observation of speed-dependent inhomogeneous profiles 98
III.4.2 Basic speed-dependent profiles 107
III.4.3 The Rautian Sobelman model 114
III.4.4 The Keilson Storer memory model 125
III.5 Ab initio approaches of the line shape 138
III.5.1 The Waldmann Snider kinetic equation 139
III.5.2 The generalized Hess method 141
III.5.3 Collision kernel method 143
III.5.4 Approaches from a simplified Waldmann Snider equation 147
III.6 New achievements since 2008 152
III.6.1 Direct prediction from molecular dynamics simulations 153
III.6.2 Using a kinetic equation 154
III.6.3 Relativistic and dispersion corrections to line-shape models 158
III.6.4 Phenomenological line-shape models 159
III.6.5 Pressure-broadening and -shifting coefficients 163
III.6.6 Available data 169
III.7 Conclusion 173
Appendix III.A Computational aspects 174
III.A1 Algorithms for the Voigt and Galatry profiles 175
III.A2 Computation of speed-dependent profiles 177

IV. Collisional line mixing (within clusters of lines) 181

IV.1 Introduction 181
IV.2 The spectral shape 189
IV.2.1 Approximations and general expressions 189
IV.2.2 Asymptotic expansions 194
IV.2.3 Computational aspects and recommendations 205
 Contents ix

IV.3 Constructing the impact relaxation matrix 210

IV.3.1 Simple empirical (classical) approaches 211
IV.3.2 Statistically based energy gap fitting laws 218
IV.3.3 Dynamically based scaling laws 226
IV.3.4 Semiclassical models 239
IV.3.5 Quantum models 251
IV.4 Determining line-mixing parameters from experiments 260
IV.4.1 Introduction 260
IV.4.2 Relaxation matrix elements 264
IV.4.3 First-order line-coupling coefficients 266
IV.4.4 Mixed theoretical model and measured spectra fitting approaches 269
IV.5 Literature review 269
IV.5.1 Available line-mixing data 270
IV.5.2 Comparisons between predictions and laboratory measurements 271
IV.5.3 Comparisons between predictions and atmospheric measurements 273
IV.6 New achievements since 2008 273
IV.6.1 Requantized classical molecular dynamics simulations 274
IV.6.2 Quantal approaches 274
IV.6.3 Refined semiclassical Robert Bonamy formalism 275
IV.6.4 Fully classical formalism 276
IV.6.5 Dynamically based scaling laws 278
IV.6.6 Energy-gap fitting laws and state-to-state cross sections 279
IV.6.7 The ovaloid sphere and hard collision models 279
IV.6.8 Kochanov’s approach 279
IV.6.9 Available data 280
IV.7 Conclusion 281
Appendix IV.A Vibrational dephasing 282
Appendix IV.B Perturbed wave functions 286
Appendix IV.C Resonance broadening 287

V. The far wings (beyond the impact approximation) 291

V.1 Introduction 291
V.2 Empirical models 293
V.2.1 The χ factor approach 293
V.2.2 The tabulated continua 297
V.2.3 Other approaches 298
V.3 Far wings calculations: the quasistatic approach 299
V.3.1 General expressions 299
V.3.2 Practical implementation and typical results 302
V.3.3 The band average line shape: back to the χ factors 305
V.4 From resonance to the far wing: a perturbative treatment 308
x Contents

V.4.1 General expressions 308

V.4.2 Illustrative results 310
V.5 From resonance to the far wing: a nonperturbative treatment 311
V.5.1 General expressions 312
V.5.2 Illustrative results 314
V.6 New achievements since 2008 317
V.6.1 Direct predictions from classical molecular dynamics simulations 317
V.6.2 Non Markovian energy-corrected sudden approach 319
V.6.3 Asymptotic line shape and χ-factor empirical models 319
V.6.4 The MT_CKD water vapor continuum 320
V.6.5 Available data 322
V.7 Conclusion 327
Appendix V.A The water vapor continuum 328
V.A1 Definition, properties, and semiempirical modeling of the H2O
continuum 330
V.A2 On the origin of the water vapor continua 332
V.A3 The self- and N2-broadened continua within the ν2 band 333
V.A4 Conclusion 335

VI. Collision-induced absorption and light scattering 337

VI.1 Introduction 337
VI.2 Collision-induced dipoles and polarizabilities for diatomic molecules 337
VI.3 Collision-induced spectra in the isotropic approximation 339
VI.3.1 Two illustrative examples: H2 and N2 339
VI.3.2 Modeling of the line shape 343
VI.4 Effects of the anisotropy of the interaction potential 347
VI.4.1 Interaction potential 349
VI.4.2 Radiative coupling 349
VI.5 The importance of bound and quasibound states in CIA spectra 354
VI.6 Interference between permanent and induced dipoles (CIA)
or polarizabilities (CILS) 357
VI.6.1 Depolarized light scattering spectra of H2 and N2 358
VI.6.2 The HD problem 361
VI.6.3 Intercollisional dips 365
VI.7 New achievements since 2008 366
VI.7.1 Quantum scattering advances 366
VI.7.2 Intracollisional interference effects 367
VI.7.3 Standard binary collision treatments 368
VI.7.4 Direct predictions from classical molecular dynamics simulations 368
VI.7.5 Integrated collision-induced absorption intensities 369
VI.7.6 Available data 370
VI.8 Conclusion 371
 Contents xi

VII. Consequences for applications 375

VII.1 Introduction 375
VII.2 Basic equations 377
VII.2.1 Radiative heat transfer 377
VII.2.2 Remote sensing 380
VII.3 Isolated lines 384
VII.3.1 The basic Lorentz and Voigt profiles 384
VII.3.2 More refined isolated line profiles 388
VII.4 Line mixing within clusters of lines 392
VII.4.1 Radiative heat transfer 392
VII.4.2 Remote sensing 392
VII.5 Allowed band wings and collision-induced absorption 400
VII.5.1 Allowed band wings 400
VII.5.2 Collision-induced absorption 407
VII.6 New achievements since 2008 410
VII.6.1 Remote sensing 410
VII.6.2 Metrology 419
VII.6.3 Radiative heat transfer and climate modeling 424
VII.7 Conclusion 428

VIII. Laboratory experimental techniques 431

VIII.1 Introduction 431
VIII.2 Cavity-enhanced absorption spectroscopy 435
VIII.3 Cavity ring-down spectroscopy 437
VIII.4 Frequency comb-assisted methods 438
VIII.5 Cavity mode-width and mode-dispersion spectroscopies 439
VIII.6 Direct frequency comb spectroscopy 442
VIII.6.1 Dual comb with two femtosecond lasers 442
VIII.6.2 Dual comb with minicombs 443
VIII.6.3 Comb-based Fourier-transform spectroscopy with subnominal resolution 443
VIII.7 Cavity-enhanced direct frequency comb spectroscopy 444
VIII.8 Dual-laser absorption spectroscopy 445
VIII.9 Fourier-transform spectroscopy methods 446
VIII.10 Advances in coherent terahertz spectroscopy 447

IX. Toward future researches 449

IX.1 Introduction 449
IX.2 Dicke narrowing in speed-dependent line-mixing profiles 449
IX.2.1 Models of profiles in the hard collision frame 450
IX.2.2 Experimental tests in multiplet spectra 454
IX.3 From resonances to the far wings 460
xii Contents

IX.3.1 Semiclassical approach 461

IX.3.2 Generalized scaling approach 465
IX.4 Tomorrow’s spectroscopic databases 466
IX.5 Conclusion 470

Abbreviations and acronyms 473

Symbols 479
Units and conversions 483
References 485
Index 553
Foreword to second edition

Since the publication of Collisional Effects on Molecular Spectra: Laboratory Experiments

and Models, Consequences for Applications in 2008, considerable qualitative and quantita-
tive progress has been made on all aspects of the subjects that were discussed in the
first edition of this book. This second edition completes the information contained in
the former one by providing an overall but detailed view of these advances together
with an update of the bibliography on the subject. This rapidly growing field has
many relevant publications, and we introduce and discuss those that we are aware of
and that demonstrate new progress in one or more aspects of the research. Note that
most of the new inputs in this book were taken from the review paper Recent advances
in collisional effects on spectra of molecular gases and their practical consequences [Journal of
Quantitative Spectroscopy and Radiative Transfer vol. 213, pp. 178 227, 2018].
Dispatching the information on the progress made in the last decade into the fine
structure of the previous version of this book would have been a considerable work
requiring an amount of time which was beyond the author’s availabilities. The choices
that have thus been made, and the differences between this second edition and the
former one, are the following:
New sections, entitled “New achievements since 2008,” have been inserted before
the conclusions of Chapters 3 7, presenting recent results on the topics of Isolated
Lines, Line-Mixing, The Far Wings, Collision-Induced Absorption, and Consequences for
Applications, respectively. The conclusions and introductions of these chapters have
been modified accordingly. Note that, in order to keep the length of this second
edition reasonable, the added sections contain no equations and are restricted to
descriptions of results of the last decade (  2008 19) with citations to the relevant
bibliography.
A new chapter (8) was created, based on Section 2 of the abovementioned review
paper, which discusses some recently developed and/or widely used Laboratory
Experimental Techniques.
The last chapter Toward Future Researches has been amended and complemented.
Pointers toward the new sections have been inserted at relevant places within the
text of the first edition and vice versa.
The lists of Abbreviations and the Subject Index have been updated.
The new references associated with these updates have been introduced in the text
and added at the end of the former Reference List with numbers starting from the
number 932.

xiii
xiv Foreword to second edition

The present edition includes, with respect to the previous one, significant amounts
of new information, including 23 figures, 8 tables and nearly 700 references, resulting
in an increase of the overall length of the book by more than 30%.
Foreword

Remote sensing is based entirely on spectroscopy. For astronomy or atmospheric sci-

ence the physical and chemical properties of a distant object are all derived from the
interpretation of spectra. The simulation of atomic and molecular spectra requires at a
minimum line positions, line intensities, and line shapes, regardless of the state of
aggregation or spectral resolution. The position and intensity of a line or band are rela-
tively straightforward to measure or even calculate with modern quantum mechanical
methods. In contrast, the line shape or band shape is very difficult to model in part
because it depends in a very complex way on the particular environment.
The study of line shapes is a venerable subject that predates quantum mechanics
and yet is still a vigorous area of experimental and theoretical activity. Over the years
a variety of sophisticated theoretical models and approaches have been developed to
model spectral shapes of gases, but the subject has been relatively obscure. This has all
changed in recent years because of the tremendous advances in spectroscopic instru-
mentation. For example, with tunable single frequency lasers the intrinsic line shape
can be measured with a signal-to-noise ratio of several thousand in the laboratory and
with Fourier-transform spectrometers signal-to-noise ratios of several hundred are rou-
tinely obtained for atmospheric remote sensing. With such high spectral resolution
and high-quality spectra, none of the simple line shape functions reproduce the obser-
vations except at very low pressures.
The traditional favorite general-purpose line profile is the Voigt function, which
includes the Gaussian and Lorentzian functions as special limiting cases. Modern high qual-
ity spectra are then said to need “non-Voigt” line shape functions in order to be modeled
correctly. The physical source of this non-Voigt behavior may originate from many com-
plex effects including collision-induced absorption, collisional line mixing, line shape fail-
ure in the far wings (weak collisions), and a variety of other speed-dependent collisional
effects (e.g., Dicke narrowing). Collisions are hard to model correctly!
What has happened in the last few years is that the study of spectral shapes has chan-
ged from being a specialized research subject of a small group of physicists to being a
necessary tool in a much wider community. Astronomers, atmospheric scientists, com-
bustion scientists, and chemists who deal with modern high-quality spectra all encoun-
ter non-Voigt line shapes. It is therefore very timely to have this monograph by J.-M.
Hartmann, Ch. Boulet, and D. Robert; it should find wide acceptance and utility.

Peter Bernath
Department of Chemistry, University of York, York, United Kingdom

xv
Acknowledgments

The authors are three successive links of a researchers chain which was initiated by
Louis Galatry. They take the opportunity to express to him their deep gratitude for
opening a path which has led, many years later, to the writing of this monograph.
They are pleased that a link has been added to this chain about a decade ago, through
the nomination of Ha Tran as permanent scientist, and they hope that new permanent
researchers will soon complete this chain.
They express their gratitude to their colleagues who helped to complete the first
edition of this book by providing data and figures, but also by their careful readings
and suggested improvements to the first edition. Among these, special thoughts go to
Jeanine Bonamy, Lionel Bonamy, Jean-Pierre Bouanich, Roman Ciurylo, Athéna
Coustenis, Robert Gamache, Claude Girardet, Pierre Joubert, Bruno Lavorel,
Massimo Moraldi, Jean-Pierre Perchard, François Rohart, Franck Thibault, Richard
Tipping, Ha Tran, and Jean-Marie Vigoureux for reviewing parts of this book. More
generally, the authors thank all the research workers with whom they collaborated in
the past and who, directly or indirectly, contributed to the some of the results pre-
sented thereafter. Gratitude also goes to Peter Bernath for his writing of the foreword
and to Martine Bresson-Rosenmann for typing parts of this book. The new material
introduced in this second edition is largely based on the content of the review paper
Recent advances in collisional effects on spectra of molecular gases and their practical consequences,
by J.-M. Hartmann, H. Tran, R. Armante, C. Boulet, A. Campargue, F. Forget,
L. Gianfrani, I. Gordon, S. Guerlet, M. Gustafsson, J. Hodges, S. Kassi, D. Lisak,
F. Thibault and G. Toon, that was published in the Journal of Quantitative Spectroscopy
and Radiative Transfer (volume 213, pp. 178 227, 2018). We warmly thank all the
coauthors of this article for their contributions to this review and, subsequently, to this
second edition.
Jean-Michel Hartmann is grateful to his wife Laurence and to his children Sarah,
Léna, and Raphaël, who kindly supported him while he was writing this book. He
also thanks his parents who helped him all the way through the long studies which led
him to a permanent research position.
Christian Boulet thanks all those close to him, and particularly Marie-José, Valérie,
and Martial for their encouragement, support, and forbearance during the considerable
gestation period of this book, that is, the last 20 years.
Daniel Robert wishes to express his hearty gratitude to his wife Suzanne for con-
stant encouragement throughout this work. He also thanks Franck Thibault for his
kind and helpful hospitality during many short stays at Rennes University.

xvii
xviii Acknowledgments

The three authors thank the French research system (Ministère de l’Enseignement
Supérieur et de la Recherche and Centre National de la Recherche Scientifique) for providing
salaries and freedom of mind.
CHAPTER I

Introduction

Gas phase molecular spectroscopy is a field of chemical physics that was born about
150 years ago. In spite of this long history, it remains an active discipline to which
many international conferences and journals are devoted, fed by a large community of
research workers. The reasons for the vitality of this field are many, among which
one finds, in the last decades, the great improvement of experimental devices and
the growing concern about the influence of human activities on the evolution of the
Earth’s atmosphere. Modern laboratory measurements, thanks to their considerable
sensitivity, enable the study of smaller and smaller details of molecule radiation inter-
actions, thus requiring a constant improvement of the understanding and modeling of
the processes involved. The very high spectral resolution and signal-to-noise ratio
achieved by laser absorption experiments now permit the identification of refined
mechanisms which affect local features of the spectral shape at a level below one per
thousand. Their proper modeling is a challenge which requires improved theoretical
approaches (and the relevant input data), in terms of the quality of predictions for the
most important processes involved, but also of the number of mechanisms which must
be taken into account. The urgent need for a better understanding of the different
phenomena driving the Earth’s atmospheric system, which has led to large interna-
tional efforts in the development of remote sensing experiments, is another reason for
the stimulation of spectroscopic research. Today’s Fourier transform satellite-borne
instruments, for instance, provide very large amounts of spectral information at ever
increasing quality in terms of spectral coverage, resolution, and signal-to-noise ratio.
The treatment of these data and the accuracy requirements for the development of
atmospheric physics models result in the need to constantly improve the quality and
scope of the spectroscopic knowledge used for the simulation (and inversion) of mea-
sured spectra. This not only calls for increased accuracy of the spectroscopic para-
meters, but also for studies of new spectral regions and/or molecular species whose
inclusion in the remote sensing process brings new or complementary information of
the atmospheric state. The vastness of the problem is illustrated by Fig. I.1, where an
atmospheric transmission spectrum is displayed. This plot shows the richness of infor-
mation brought by modern sounding instruments and the subsequent considerable
amount of spectroscopic knowledge required for the modeling of the signatures of
the numerous species (including H2O, CO2, O3, CH4, HNO3, etc.) contributing to
the measured spectrum.

Collisional Effects on Molecular Spectra r 2021 Elsevier B.V.

DOI: https://doi.org/10.1016/B978-0-12-822364-2.00001-5 All rights reserved. 1
2 Collisional Effects on Molecular Spectra

1.0

0.8

0.6

0.4
Transmission

0.2

0.0
1100 1105 1110 1115 1120 3000 3005 3010 3015 3020

1.0
0.8
0.6
0.4
0.2
0.0
1000 1500 2000 2500 3000 3500 4000
V(cm–1)
Figure I.1 Transmission of the Earth’s atmosphere, versus wavenumber, as measured by the
satellite-based Fourier transform instrument of the Atmospheric Chemistry Experiment1 when look-
ing to a tangent height (Fig. VII.2C) of about 22 km. Courtesy P. Bernath.

The first (basic) parameters governing the interactions between molecules and elec-
tromagnetic fields are the internal energy levels and the matrix elements of the rele-
vant tensor (electric dipole, quadrupole, polarizability, etc.) responsible for the
coupling between radiation and matter. These quantities translate into the frequencies
and integrated intensities of the optical transitions. They manifest themselves, in the
spectral domain, through the positions and the areas of the absorption/emission lines,
whereas they are involved in the relative evolution and amplitude of the signal in time
domain experiments. These spectroscopic data (energies and optical transition
moments) are intrinsic characteristics of each molecular species and are thus tied to the
isolated molecule, regardless of its environment. They bring information on the geom-
etry and charge distribution but also on the internal forces within the ensemble of par-
ticles composing the considered molecule. They are the first quantities to be known
for any modeling of gas radiation interactions. For these reasons, they have been, and
still are, the subject of many researches leading to the constant improvement of widely
used molecular spectroscopic databases.2 5 These progresses result from experimental
efforts which provide, through laser and spectrometer laboratory techniques,6 12 the
spectral signatures of the various molecular transitions (rotational, vibrational, elec-
tronic, etc.) induced by the interaction with the electromagnetic field. From the
Another random document with
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 SWEET CARROTS. (ENTREMETS.)

Boil quite tender some fine highly-flavoured carrots, press the

water from them, and rub them through the back of a fine hair-sieve;
put them into a clean saucepan or stewpan, and dry them thoroughly
over a gentle fire; then add a slice of fresh butter, and when this is
dissolved and well mixed with them, strew in a dessertspoonful or
more of powdered sugar, and a little salt; next, stir in by degrees
some good cream, and when this is quite absorbed, and the carrots
again appear dry, dish and serve them quickly with small sippets à la
Reine (see page 5), placed round them.
Carrots, 3 lbs., boiled quite tender: stirred over a gentle fire 5 to 10
minutes. Butter, 2 oz.; salt, 1/2 teaspoonful; pounded sugar, 1
dessertspoonful; cream, 1/2 pint, stewed gently together until quite
dry.
Obs.—For excellent mashed carrots omit the sugar, add a good
seasoning of salt and white pepper, and half a pint of rich brown
gravy; or for a plain dinner rather less than this of milk.
 MASHED (OR BUTTERED) CARROTS.

(A Dutch Receipt.)
Prepare some finely flavoured carrots as above, and dry them
over a gentle fire like mashed turnips; then for a dish of moderate
size mix well with them from two to three ounces of good butter, cut
into small bits, keeping them well stirred. Add a seasoning of salt
and cayenne, and serve them very hot, garnished or not at pleasure
with small sippets (croutons) of fried bread.
 CARROTS AU BEURRE, OR BUTTERED CARROTS.

(French.)
Either boil sufficient carrots for a dish quite tender, and then cut
them into slices a quarter of an inch thick, or first slice, and then boil
them: the latter method is the most expeditious, but the other best
preserves the flavour of the vegetable. Drain them well, and while
this is being done just dissolve from two to three ounces of butter in
a saucepan, and strew in some minced parsley, some salt, and white
pepper or cayenne; then add the carrots, and toss them very gently
until they are equally covered with the sauce, which should not be
allowed to boil: the parsley may be omitted at pleasure. Cold carrots
may be re-warmed in this way.
 CARROTS IN THEIR OWN JUICE.

(A simple but excellent Receipt.)

By the following mode of dressing carrots, whether young or old,
their full flavour and all the nutriment they contain are entirely
preserved; and they are at the same time rendered so palatable by it
that they furnish at once an admirable dish to eat without meat, as
well as with it. Wash the roots very clean, and scrape or lightly pare
them, cutting out any discoloured parts. Have ready boiling and
salted, as much water as will cover them; slice them rather thick,
throw them into it, and should there be more than sufficient to just
float them (and barely that), pour it away. Boil them gently until they
are tolerably tender, and then very quickly, to evaporate the water, of
which only a spoonful or so should be left in the saucepan. Dust a
seasoning of pepper on them, throw in a morsel of butter rolled in
flour, and turn and toss them gently until their juice is thickened by
them and adheres to the roots. Send them immediately to table.
They are excellent without any addition but the pepper; though they
may be in many ways improved. A dessertspoonful of minced
parsley may be strewed over them when the butter is added, and a
little thick cream mixed with a small proportion of flour to prevent its
curdling, may be strewed amongst them, or a spoonful or two of
good gravy.
 TO BOIL PARSNEPS.

These are dressed in precisely the same manner as carrots, but

require much less boiling. According to their quality and the time of
year, they will take from twenty minutes to nearly an hour. Every
speck or blemish should be cut from them after they are scraped,
and the water in which they are boiled should be well skimmed. They
are a favourite accompaniment to salt fish and boiled pork, and may
be served either mashed or plain.
20 to 25 minutes.
 FRIED PARSNEPS.

Boil them until they are about half done, lift them out, and let them
cool; slice them rather thickly, sprinkle them with fine salt and white
pepper, and fry them a pale brown in good butter. Serve them with
roast meat, or dish them under it.
 JERUSALEM ARTICHOKES.

Wash the artichokes, pare them quickly, and throw them as they
are done into a saucepan of cold water, or of equal parts of milk and
water; and when they are about half boiled add a little salt to them.
Take them up the instant they are perfectly tender: this will be in from
fifteen to twenty-five minutes, so much do they vary in size and as to
the time necessary to dress them. If allowed to remain in the water
after they are done, they become black and flavourless. Melted
butter should always be sent to table with them.
15 to 25 minutes.
 TO FRY JERUSALEM ARTICHOKES. (ENTREMETS.)

Boil them from eight to twelve minutes; lift them out, drain them on
a sieve, and let them cool; dip them into beaten eggs, and cover
them with fine bread-crumbs. Fry them a light brown, drain, pile them
in a hot dish, and serve them quickly.
 JERUSALEM ARTICHOKES, À LA REINE.

Wash and wipe the

artichokes, cut off one end of
each quite flat, and trim the
other into a point; boil them in
milk and water, lift them out the
instant they are done, place Artichokes à la Reine.
them upright in the dish in which
they are to be served, and
sauce them with a good béchamel, or with nearly half a pint of cream
thickened with a rice-crustspoonful of flour, mixed with an ounce and
a half of butter, and seasoned with a little mace and some salt. When
cream cannot be procured use new milk, and increase the proportion
of flour and butter.
 MASHED JERUSALEM ARTICHOKES.

Boil them tender, press the water well from them, and then
proceed exactly as for mashed turnips, taking care to dry the
artichokes well, both before and after the milk or cream is added to
them; they will be excellent if good white sauce be substituted for
either of these.
 HARICOTS BLANCS.

The haricot blanc is the seed of a particular kind of French bean,

of which we find some difficulty in ascertaining the English name, for
though we have tried several which resembled it in appearance, we
have found their flavour, after they were dressed, very different, and
far from agreeable. The large white Dutch runner, is, we believe, the
proper variety for cooking; at least we have obtained a small quantity
under that name, which approached much more nearly than any
others we had tried to those which we had eaten abroad. The
haricots, when fresh may be thrown into plenty of boiling water, with
some salt and a small bit of butter; if dry, they must be previously
soaked for an hour or two, put into cold water, brought to boil gently,
and simmered until they are tender, for if boiled fast the skins will
burst before the beans are done. Drain them thoroughly from the
water when they are ready, and lay them into a clean saucepan over
two or three ounces of fresh butter, a small dessertspoonful of
chopped parsley, and sufficient salt and pepper to season the whole;
then gently shake or toss the beans until they are quite hot and
equally covered with the sauce; add the strained juice of half a
lemon, and serve them quickly. The vegetable thus dressed, is
excellent; and it affords a convenient resource in the season when
the supply of other kinds is scantiest. In some countries the dried
beans are placed in water, over-night, upon a stove, and by a very
gentle degree of warmth are sufficiently softened by the following
day to be served as follows:—they are drained from the water,
spread on a clean cloth and wiped quite dry, then lightly floured and
fried in oil or butter, with a seasoning of pepper and salt, lifted into a
hot dish, and served under roast beef, or mutton.
 TO BOIL BEET ROOT.

Wash the roots delicately clean, but neither scrape nor cut them,
for should even the small fibres be taken off before they are cooked,
their beautiful colour would be much injured. Throw them into boiling
water, and, according to their size, which varies greatly, as they are
sometimes of enormous growth, boil them from one hour and a half
to two and a half, or longer if requisite. Pare and serve them whole,
or cut into thick slices and neatly dished in a close circle: send
melted butter to table with them. Cold red beet root is often
intermingled with other vegetables for winter salads; and it makes a
pickle of remarkably brilliant hue. A common mode of serving it at
the present day is in the last course of a dinner with the cheese: it is
merely pared and sliced after having been baked or boiled tender.
1-1/2 to 2-1/2 hours, or longer.
 TO BAKE BEET ROOT.

Beet root if slowly and carefully baked until it is tender quite

through, is very rich and sweet in flavour, although less bright in
colour than when it is boiled: it is also, we believe, remarkably
nutritious and wholesome. Wash and wipe it very dry, but neither cut
nor break any part of it; then lay it into a coarse earthen dish, and
bake it in a gentle oven for four or five hours: it will sometimes
require even a longer time than this. Pare it quickly if it be served
hot; but leave it to cool first, when it is to be sent to table cold.
In slow oven from 4 to 6 hours.
 STEWED BEET ROOT.

Bake or boil it tolerably tender, and let it remain until it is cold, then
pare and cut it into slices; heat and stew it for a short time in some
good pale veal gravy (or in strong veal broth for ordinary occasions),
thicken this with a teaspoonful of arrow-root, and half a cupful or
more of good cream, and stir in, as it is taken from the fire, from a
tea to a tablespoonful of chili vinegar. The beet root may be served
likewise in thick white sauce, to which, just before it is dished, the
mild eschalots of page 128 may be added.
 TO STEW RED CABBAGE.

(Flemish Receipt.)
Strip the outer leaves from a fine and fresh red cabbage; wash it
well, and cut it into the thinnest possible slices, beginning at the top;
put it into a thick saucepan in which two or three ounces of good
butter have been just dissolved; add some pepper and salt, and stew
it very slowly indeed for three or four hours in its own juice, keeping it
often stirred, and well pressed down. When it is perfectly tender add
a tablespoonful of vinegar; mix the whole up thoroughly, heap the
cabbage in a hot dish, and serve broiled sausages round it; or omit
these last, and substitute lemon-juice, cayenne pepper, and a half-
cupful of good gravy.
The stalk of the cabbage should be split in quarters and taken
entirely out in the first instance.
3 to 4 hours.
 BRUSSELS SPROUTS.

These delicate little sprouts, or miniature cabbages, which at their

fullest growth scarcely exceed a large walnut in size, should be quite
freshly gathered. Free them from all discoloured leaves, cut the
stems even, and wash the sprouts thoroughly. Throw them into a
pan of water properly salted, and boil them quickly from eight to ten
minutes; drain them well, and serve them upon a rather thick round
of toasted bread buttered on both sides. Send good melted butter to
table with them. This is the Belgian mode of dressing this excellent
vegetable, which is served in France with the sauce poured over it,
or it is tossed in a stewpan with a slice of butter and some pepper
and salt: a spoonful or two of veal gravy (and sometimes a little
lemon-juice) is added when these are perfectly mixed.
8 to 10 minutes.
 SALSIFY.

We are surprised that a vegetable so excellent as this should be

so little cared for in England. Delicately fried in batter—which is a
common mode of serving it abroad—it forms a delicious second
course dish: it is also good when plain-boiled, drained, and served in
gravy, or even with melted butter. Wash the roots, scrape gently off
the dark outside skin, and throw them into cold water as they are
done, to prevent their turning black; cut them into lengths of three or
four inches, and when all are ready put them into plenty of boiling
water with a little salt, a small bit of butter, and a couple of spoonsful
of white vinegar or the juice of a lemon: they will be done in from
three quarters of an hour to an hour. Try them with a fork, and when
perfectly tender, drain, and serve them with white sauce, rich brown
gravy, or melted butter.
3/4 to 1 hour.
 FRIED SALSIFY. (ENTREMETS.)

Boil the salsify tender, as directed above, drain, and then press it
lightly in a soft cloth. Make some French batter (see Chapter V.),
throw the bits of salsify into it, take them out separately, and fry them
a light brown, drain them well from the fat, sprinkle a little fine salt
over them after they are dished, and serve them quickly. At English
tables, salsify occasionally makes its appearance fried with egg and
bread-crumbs instead of batter. Scorgonera is dressed in precisely
the same manner as the salsify.
 BOILED CELERY.

This vegetable is extremely good dressed like sea-kale, and

served on a toast with rich melted butter. Let it be freshly dug, wash
it with great nicety, trim the ends, take off the coarse outer-leaves,
cut the roots of equal length, tie them in bunches, and boil them in
plenty of water, with the usual proportion of salt, from twenty to thirty
minutes.
20 to 30 minutes.
 STEWED CELERY.

Cut five or six fine roots of celery to the length of the inside of the
dish in which they are to be served; free them from all the coarser
leaves, and from the green tops, trim the root ends neatly, and wash
the vegetable in several waters until it is as clean as possible; then,
either boil it tender with a little salt, and a bit of fresh butter the size
of a walnut, in just sufficient water to cover it quite, drain it well,
arrange it on a very hot dish, and pour a thick béchamel, or white
sauce over it; or stew it in broth or common stock, and serve it with
very rich, thickened, Espagnole or brown gravy. It has a higher
flavour when partially stewed in the sauce, after being drained
thoroughly from the broth. Unless very large and old, it will be done
in from twenty-five to thirty minutes, but if not quite tender, longer
time must be allowed for it. A cheap and expeditious method of
preparing this dish is to slice the celery, to simmer it until soft in as
much good broth as will only just cover it, and to add a thickening of
flour and butter, or arrow-root, with some salt, pepper, and a small
cupful of cream.
25 to 30 minutes, or more.