Laboratory Astrochemistry: From Molecules through Nanoparticles to Grains

531 Pages·2015·7.194 MB·English

by  Stephan Schlemmer (editor), Thomas Giesen (editor), Harald Mutschke (editor), Cornelia Jäger (editor)

Editedby
StephanSchlemmer,ThomasGiesen,
HaraldMutschke,andCorneliaJäger
LaboratoryAstrochemistry
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EditedbyStephanSchlemmer,ThomasGiesen,
HaraldMutschke,andCorneliaJäger
Laboratory Astrochemistry
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V
Contents
ListofContributors XIII
Preface XIX
1 TheAstrophysicalBackground 1
MalcolmWalmsley
1.1 TheContentsofthisVolume 8
References 11
2 MolecularSpectroscopy 13
ThomasGiesen
2.1 ElectronicSpectroscopyofPotentialCarriersofDiffuseInterstellar
Bands 15
CoreyA.RiceandJohnP.Maier
2.1.1 Introduction 15
2.1.2 LaboratoryMethods 16
2.1.2.1 ResonantTwo-ColorTwo-PhotonIonization 17
2.1.2.2 ResonantTwo-ColorPhotodetachment 17
2.1.2.3 ResonantTwo-Color,Two-PhotonFragmentation 17
2.1.2.4 CavityRingdownSpectroscopy 18
2.1.2.5 Four-WaveMixingTechnique 18
2.1.2.6 Laser-InducedFluorescence 18
2.1.3 SpeciesofAstrophysicalInterest 19
2.1.3.1 MolecularIons 19
2.1.3.2 BareCarbonChains 22
2.1.3.3 Metal-ContainingCarbonChains 24
2.1.4 Outlook 28
Acknowledgments 29
2.2 UV–VisGas-PhaseAbsorptionSpectroscopyofPAHs 29
YvainCarpentier,GaëlRouillé,MathiasSteglich,CorneliaJäger,Thomas
Henning,andFriedrichHuisken
2.2.1 Introduction 29
2.2.2 Experimental 32
2.2.2.1 SupersonicJetCavityRingdownSpectrometer 32
VI Contents
2.2.2.2 Matrix-IsolationSpectroscopy 35
2.2.3 DataAnalysis 36
2.2.3.1 DerivationofAbsorptionCrossSections 36
2.2.3.2 ExtrapolationofGas-PhaseTransitionsfromMISData 39
2.2.4 ResultsandDiscussion 40
2.2.5 Conclusion 48
Acknowledgments 49
2.3 LaboratoryIRSpectroscopyofPAHs 49
JosOomens,OlivierPirali,andAlexanderG.G.M.Tielens
2.3.1 Introduction 49
2.3.2 LaboratorySpectroscopicMethods 52
2.3.2.1 NeutralPAHs 53
2.3.2.2 CationicPAHs 54
2.3.2.3 Computational 58
2.3.2.4 ComparisonofExperimentalMethods 58
2.3.3 Far-InfraredSpectroscopy 60
2.3.3.1 LaboratoryResults 61
2.3.4 IRSpectralFeaturesofPAHs 63
2.3.5 PAHDerivativesandRelatedSpecies 64
2.3.5.1 Nitrogen-SubstitutedPAHs 65
2.3.5.2 ProtonatedPAHs 65
2.3.5.3 HydrogenatedandDehydrogenatedPAHs 66
2.3.5.4 Metal–PAHComplexes 67
2.3.5.5 OtherPAHModifications 67
2.3.6 Conclusions 68
2.4 TheSpectroscopyofComplexMolecules 68
HolgerS.P.Müller
2.4.1 Introduction 68
2.4.2 GeneralSpectroscopicConsiderations 69
2.4.3 TheQuestforInterstellarGlycine 72
2.4.4 GeneralAstronomicConsiderations 73
2.4.5 AlkylAlcohols 77
2.4.5.1 Methanol,CH OH 77
3
2.4.5.2 Ethanol,C H OH 79
2 5
2.4.5.3 Largeralkanols 81
2.4.5.4 Alkanediolsand-polyols 82
2.4.6 AlkylEthers 83
2.4.6.1 Dimethyl,EtherCH OCH 84
3 3
2.4.6.2 LargerEthers 86
2.4.7 Esters 87
2.4.8 AlkylCyanides 89
2.4.9 OtherComplexMolecules 91
References 97
Contents VII
3 GasPhaseChemistry 109
StephanSchlemmer
3.1 Introduction 109
3.1.1 CrossSectionsandRateCoefficientsforBinaryCollisions 117
3.1.2 DifferentialScatteringandCrossedBeamExperiments 123
3.1.3 Low-EnergyCollisionsinMergedBeamsandIntegralCross
Sections 128
3.1.4 Low-TemperatureCollisionsinBeamsandTraps,ThermalRate
Coefficients 132
3.1.4.1 SelectedIonFlowTubes 134
3.1.4.2 LavalNozzleExpansions 136
3.1.4.3 TrapExperiments 139
Acknowledgment 143
3.2 DissociativeRecombination 143
WolfGeppert,AndreasWolf,andJurajGlosik
3.2.1 PrincipleandMainOccurrence 143
3.2.1.1 MechanismsofDissociativeRecombination 144
3.2.1.2 DissociativeRecombinationinAstronomicalEnvironments 146
3.2.2 MethodsofLaboratoryStudy 151
3.2.2.1 MulticollisionalSwarmMethods 151
3.2.2.2 Single-CollisionBeamMethods 154
3.2.3 RecentLaboratoryResultsandtheirImpactonMolecular
Astrophysics 157
3.2.3.1 DRoftheTriatomicHydrogenIonH+ 157
3
3.2.3.2 BranchingRatiosandInternalExcitationforMolecularFragments
fromDR 159
3.2.3.3 DRandFormationofInterstellarMethanol 160
3.2.3.4 DRofProtonatedNitrilesinTitan’sIonosphere 162
3.3 InelasticProcesses 163
DavidParkerandLaurentWiesenfeld
3.3.1 Introduction 163
3.3.2 MolecularBeamMeasurementsofInelasticScatteringin
Water 164
3.3.3 LaserIonizationofMolecularHydrogenandNascentWater 168
3.3.4 ExperimentalDetails 169
3.3.4.1 DensitytoFluxCorrectionandRelativeCollisionCross
Sections 169
3.3.4.2 TemperatureControl 170
3.3.5 CalculatingDifferentialandTotalCrossSections 171
3.3.6 Water–HydrogenMoleculePES 172
3.3.7 DynamicalCalculations 174
3.3.7.1 TotalCrossSectionsandRates 174
3.3.7.2 DifferentialCrossSections 174
3.3.8 TheoryandExperimentsComparisons 175
3.3.8.1 DifferentialCrossSections 175
VIII Contents
3.3.8.2 TotalCrossSections 177
3.3.8.3 OtherScatteringExperiments 178
3.4 LowTemperatureTrappingExperiments 179
OskarAsvanyandStephanSchlemmer
3.4.1 N++H 181
2
3.4.2 H++H 184
3 2
3.4.3 DeuteriumFractionation 190
3.4.4 TrapExperimentsonDeuteriumEnrichment 195
3.4.5 TowardState-to-StateRateCoefficients 202
3.5 NegativeIonChemistryintheEarlyUniverse 205
HolgerKreckelandDanielWolfSavin
3.5.1 Introduction:NegativeIonsinSpace 205
3.5.2 TheChemistryoftheEarlyUniverse 206
3.5.3 H FormationbyAssociativeDetachmentofH−andH 208
2
3.5.4 H−Photodetachment 215
3.5.5 MutualNeutralizationofH−andH+ 216
3.5.6 Summary 218
Acknowledgments 219
References 219
4 MolecularPhotodissociation 229
EwineF.vanDishoeckandRuudVisser
4.1 Introduction 229
4.2 PhotodissociationProcesses 230
4.2.1 SmallMolecules 230
4.2.2 LargeMolecules 233
4.3 PhotodissociationCrossSections 234
4.3.1 Theory 234
4.3.1.1 Born–Oppenheimerapproximation 235
4.3.1.2 ElectronicEnergies:MethodofConfigurationInteraction 236
4.3.1.3 NuclearDynamics:OscillatorStrengthsandCrossSections 237
4.3.2 Experiments 238
4.3.3 PhotodissociationProducts 240
4.4 AstrophysicalRadiationFields 242
4.4.1 GeneralInterstellarRadiationField 242
4.4.2 StellarRadiationFields 243
4.4.3 LymanαRadiation 244
4.4.4 Cosmic-Ray-InducedPhotons 244
4.4.5 DustAttenuation 245
4.4.6 Self-Shielding 246
4.5 PhotodissociationRates 246
4.6 PhotodissociationofCOanditsIsotopologs 247
4.7 PhotostabilityofPAHs 249
4.8 Summary 251