Weakly Interacting Molecular Pairs: Unconventional Absorbers of Radiation in the Atmosphere

294 Pages·2003·8.51 MB·English

by  M. Gustafsson

Weakly Interacting Molecular Pairs: Unconventional
Absorbers of Radiation in the Atmosphere
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Series IV: Earth and Environmental Sciences - Vol. 27
Weakly Interacting Molecular
Pairs: Unconventional Absorbers
of Radiation in the Atmosphere
edited by
Claude Camy-Peyret
Universite Pierre et Marie Curie & CNRS,
Paris, France
and
Andrei A. Vigasin
Wave Research Center, General Physics Institute,
Russian Academy of Sciences, Moscow, Russia
1IrI...
"
Springer-Science+Susiness Media, S.v.
Proceedings of the NATO Advanced Research Workshop on
Weakly Interacting Molecular Pairs: Unconventional Absorbers of Radiation in the
Atmosphere
Fontevraud, France
29 April-3 May, 2002
A C.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-1-4020-1596-0 ISBN 978-94-010-0025-3 (eBook)
DOI 10.1007/978-94-010-0025-3
Printed on acid-free paper
All Rights Reserved
© 2003 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 2003
Softcover reprint of the hardcover 1st edition 2003
No part of this work may be reproduced, stored in a retrieval system, or transmitted in any
form or by any means, electronic, mechanical, photocopying, microfilming, recording or
otherwise, without written permission from the Publisher, with the exception of any
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ter system, for exclusive use by the purchaser of the work.
Contents
Preface xi
ContributingAuthors xv
Part I THEORY
SPECTRAOFTWO-ANDTHREE-BODY
VANDERWAALSCOMPLEXES 3
M.Gustafsson, L.Frommhold
1 Introductoryremarks 3
2 Supramolecularproperties 4
3 Supramolecularspectra 8
BIMOLECULARABSORPTIONINATMOSPHERICGASES 23
A.A.Vigasin
1 Introduction 23
2 Statisticalmechanicsofinteractingmolecules 26
3 Howbimolecular statesshowupinabsorption 34
4 Conclusions 44
TRAJECTORYSTUDY
OFCO2–ArANDCO2–HeCOLLISIONCOMPLEXES 49
S.V.Ivanov
1 Introduction 49
2 Classical trajectoryequationsforatom-diatom collision 50
3 Intermolecularinteractionpotential 53
4 Computationalprocedure 53
5 Resultsofsimulation 54
6 Conclusions 61
THEORETICALSTUDYOFINTERACTIONPOTENTIAL
ANDPRESSUREBROADENINGOFSPECTRALLINES
FORTHEHe–CH3FCOMPLEX 65
B.Bussery-Honvault, J.Boissoles,R.Moszynski
VARIATIONALSOLUTIONOFANHARMONICVIBRATIONAL
PROBLEMSFORPOLYATOMICSANDMOLECULARPAIRS 73
A.I.Pavlyuchko,B.S.Orlinson,A.A.Vigasin
1 Generaloutline 73
2 Casestudyofthecarbondioxidecomplexes 77
v
vi WEAKLY INTERACTING MOLECULAR PAIRS
INTERFERENCEEFFECTS INTHEINFRAREDSPECTRUMOFHD 83
G.C.Tabisz
1 Introduction 83
2 Interference 84
3 Experimentalevidence 84
4 Collisional propagation 86
5 Calculations 88
6 Dipolemomentcomponents 89
7 Planetaryatmospheres 90
8 Summaryandneedsforfuture 91
COLLISION-INDUCEDABSORPTION
INDIPOLARMOLECULE–HOMONUCLEARDIATOMICPAIRS 93
A.Brown,R.H.Tipping
1 Introduction 93
2 Theory 94
3 Resultsanddiscussion 95
4 Conclusions 97
CLUSTERING,SATURATEDVAPORS,ANDTHEATMOSPHERE:
THE(H2O)n,H2O–N2,ANDH2O–O2 CASES 101
Z.Slanina,F.Uhl´ık
1 Introduction 101
2 Simpledimerization case 102
3 Clustersofanydimension 103
4 H2O–N2 andH2O–O2 hetero-dimers 105
EQUILIBRIUMCONSTANTSFORTHEFORMATION
OFWEAKLYBOUNDDIMERS 111
A.A.Vigasin
1 Introduction 111
2 Generaloutline 113
3 Diatomicdimers 114
4 Quantumcorrections 120
5 Polyatomic dimers 121
6 Conclusions 122
COLLISIONINDUCEDFARWINGS
OFCO2 ANDH2OBANDSINIRSPECTRA 125
M.V.Tonkov,N.N.Filippov
1 Introduction 125
2 Bandprofilestudies 126
3 Farwing approximation 127
4 Impactapproximation 130
5 H2Obandwings 133
6 Conclusions 135
FAR-WINGLINESHAPES:
APPLICATIONTOTHEWATERCONTINUUM 137
R.H.Tipping,Q.Ma
1 Introduction 137
2 Results 140
Contents vii
Part II LABORATORY STUDIES
COLLISION-INDUCEDABSORPTIONINTHECO2 FERMITRIAD
FORTEMPERATURESFROM211Kto296K 149
Y.I.Baranov,G.T.Fraser, W.J.Lafferty, A.A.Vigasin
1 Introduction 149
2 Experimental 150
3 Dataprocessing andresults 151
4 Conclusions 156
LABORATORYSTUDIESOFOXYGENCONTINUUMABSORPTION 159
Y.I.Baranov,G.T.Fraser, W.J.Lafferty, B.Mat´e,A.A.Vigasin
MOLECULARBEAMSCATTERINGEXPERIMENTS
ONSPECIESOFATMOSPHERICRELEVANCE:
POTENTIALENERGYSURFACESFORCLUSTERS
ANDQUANTUMMECHANICALPREDICTION
OFSPECTRALFEATURES 169
V.Aquilanti,M.Bartolomei,D.Cappelletti,E.Carmona-Novillo,
E.Cornicchi,M.Moix-Teixidor,M.Sabido´,F.Pirani
1 Introduction 170
2 Descriptionoftheinteraction 170
3 Clusterdynamics: boundstatesandspectralfeatures 175
4 Scatteringexperiments: simplehydrocarbonsandwater 177
COLLISION-INDUCEDABSORPTION
OFGASEOUSOXYGENINTHEHERZBERGCONTINUUM 183
M.B.Kiseleva,G.Ya.Zelikina,M.V.Buturlimova,A.P.Burtsev
1 Introduction 183
2 Experiment 184
3 Analysisoftheexperimentaldata 185
4 Discussion 188
ABSORPTIONCROSS-SECTIONOFTHECOLLISION-INDUCED
BANDSOFOXYGENFROMTHEUVTOTHENIR 193
C.Hermans,A.C.Vandaele,S.Fally,M.Carleer,R.Colin,
B.Coquart,A.Jenouvrier, M.-F.Merienne
1 Introduction 194
2 Experimental 194
3 Results 196
4 Impactonatmosphericretrievals 200
5 Summaryandconclusion 200
CAVITYRING-DOWNSPECTROSCOPY
OFO2–O2 COLLISIONALINDUCEDABSORPTION 203
M.Sneep,W.Ubachs
1 Introduction 203
2 PrinciplesofCavityRing-DownSpectroscopy 204
3 Measurementsonsmallsamples 206
4 CRDmeasurementsofoxygencollisional complexes 207
viii WEAKLY INTERACTING MOLECULAR PAIRS
LABORATORYFOURIERTRANSFORMSPECTROSCOPYOFTHE
WATERABSORPTIONCONTINUUMFROM2500 TO22500cm−1 213
M.Carleer, M.Kiseleva,S.Fally,P.-F.Coheur, C.Clerbaux, R.Colin,
L.Daumont,A.Jenouvrier, M.-F.Merienne,C.Hermans,A.C.Vandaele
1 Introduction 214
2 Experimental 214
3 Resultsanddiscussion 216
4 Conclusion 219
INFRAREDSPECTRAOFWEAKLY-BOUNDCOMPLEXES
ANDCOLLISION-INDUCEDEFFECTS
INVOLVINGATMOSPHERICMOLECULES 223
A.R.W.McKellar
1 Introduction 223
2 Linksbetweenweakly-bounddimersand“normal”spectra 224
3 Afamilyofatmospheric vanderWaals molecules,(N2)2,N2–CO,and
(CO)2 228
4 Thewater dimer,aspectroscopic challenge 230
THEFAR-INFRAREDCONTINUUM
INTHESPECTRUMOFWATERVAPOR 233
X.Wang,A.Senchuk, G.C.Tabisz
1 Introduction 233
2 Experimentalconsiderations 234
3 Continuumanalysis 235
4 Concludingremarks 235
RESONATORSPECTROSCOPYASANEWMETHOD
OFINVESTIGATIONOFUNCONVENTIONAL
MILLIMETER-WAVEATMOSPHERICABSORBERS 239
A.A.Shvetsov, M.Y.Tretyakov, M.A.Koshelev, A.F.Krupnov,V.V.Parshin
1 Introduction 239
2 Aprincipleofthewiderangemicrowaveresonatorspectroscopy 240
3 Experimentalset-up 241
4 Procedureandresultsofthemeasurements 243
5 Conclusion 245
Part III ATMOSPHERIC APPLICATIONS
LOOK-UPTABLEANDINTERPOLATIONMETHODS
FORRADIATIVETRANSFERCALCULATIONSINTHEINFRARED
APPLICATIONTOBALLOONANDSATELLITESPECTRA 249
M.Eremenko, S.Payan,Y.T´e,G.Dufour,V.Ferreira,
P.Jeseck, C.Camy-Peyret, A.Mitsel
1 Introduction 250
2 Look-uptabledescription 250
3 Comparison ofLook-uptablesinterpolationandLine-by-line
calculations 253
4 Calculation time 254
5 Applicationofwidespectralregionanalysis 257
6 Conclusions 257
Contents ix
THEIMPACTOFNEWWATERVAPORSPECTROSCOPY
ONSATELLITERETRIEVALS 259
A.N.Maurellis,R.Lang,J.E.Williams,W.J.vander Zande,K.Smith,
D.A.Newnham,J.Tennyson,R.N.Tolchenov
1 Introduction 260
2 Theatmosphereaslaboratory 261
3 Retrievaltheory 261
4 Resultsofsimulations 264
5 Newlaboratory measurementsofthewatervaporcontinuum 267
6 Conclusions 269
SPECTROSCOPICANDTHERMOCHEMICALINFORMATION
ONTHEO2-O2 COLLISIONALCOMPLEX
INFERREDFROMATMOSPHERICUV/VISIBLE
O4 ABSORPTIONBANDPROFILEMEASUREMENTS 273
K.Pfeilsticker,H.B¨osch,R.Fitzenberger, C.Camy-Peyret
1 Introduction 274
2 Observations 275
3 Discussionandconclusion 279
Index 285
Preface
The Advanced Research Workshop entitled “Weakly Interacting
Molecular Pairs: Unconventional Absorbers of Radiation in the Atmo-
sphere” was held in Abbaye de Fontevraud, France, from April 29 to
May 3, 2002. The meeting involved 40 researchers from 14 countries.
The goal of this meeting was to address a problem that the scientific
community is aware of for many years. Up now, however, the solu-
tion for this problem is far from satisfactory. Pair effects are called
unconventional in the title of this meeting. In specific spectral domains
and/or geophysical conditions they are recognized to play a dominant
role in the absorption/emission properties of the atmosphere. Water
vapor continuum absorption is among the most prominent examples.
Permanently improving accuracy of both laboratory studies and field
observations requires better knowledge of the spectroscopic features at-
tributable to molecular pairs which may form at equilibrium. The
Workshop was targeted both to clarify the pending questions and, as
farasfeasible, totracethepath topossibleanswerssincetheunderlying
phenomena are yet incompletely understood and since a reliable theory
is often not available. On the other hand, the lack of precise laboratory
data on bimolecular absorption is often precluding the construction of
reliable theoretical models. Ideally, the knowledge accumulated in the
courseoflaboratorystudiesshouldcorrelate withthepractical demands
from those who are carrying out atmospheric field measurements and
space observations.
The Workshop’ co-directors have been pursuingseveral goals. First,
we are hoping that the interested reader might be curious to discover
the state-of-the-art methods, theories and techniques used for the study
of weakly interacting molecular pairs—an interdisciplinary domain of
science. Oursecond goal is topointout at serious deficiencies inthe un-
derstanding of bimolecular phenomena occurring in the atmosphere in
order to stimulate new laboratory and theoretical investigations. Third,
our motivation is to open new ways in which laboratory measurements
and theoretical developments could be more efficiently used for remote
xi