MOLECULAR COMPLEXES IN EARTH'S, PLANETARY, COMETARY, AND INTERSTELLAR ATMOSPHERES

Transcription

1 MOLECULAR COMPLEXES IN EARTH'S, PLANETARY, COMETARY, AND INTERSTELLAR ATMOSPHERES Editors Andrei A. Vigasin Obukhov Institute of Atmospheric Physics, Russia Zdenek Slanina Toyohashi University of Technology, Japan World Scientific Singapore New Jersey London Hong Kong

2 Preface Introduction Chapter 1 General Concept Atmospheric Applications Relevant Laboratory Studies Statistical Physics and Thermodynamics of Bimolecular Complexes A. A. Vigasin 1 Introduction Equilibrium Composition of Associating Gas.1 Mass-Action Law. Partition Functions.3 Predictions Based on Intermolecular Potentials Xlll xv xvii 6 7 Bound and Metastable States of the Interacting Molecules A Set of Quantum Oscillators 3. Subdivision of Phase Space for Diatomics General Model of the Phase Space Subdivision for Polyatomic Dimers 15 Statistical Average of the Individual Characteristics of Dimers 4.1 Dissociation Energy 4. Collision-Induced Absorption in the Gas Phase 4 Integrated Intensity 5 A Case Study of the CIA Intensity Subdivision for N, O, and CO 8 3

3 viii Chapter Non-Rigidity in van der Waals Molecules: Some Case Studies R. G. A. Bone Introduction Tunneling Phenomena and Symmetry Occurrence of Argon, C H and SO in Atmospheres and the Cosmos 3.1 Argon 3. C H 3.3. SO Examples of Non-Rigidity in van der Waals Molecules 4.1 Ar-SO 4. (SO ) 4.3 (C H ) 4.4 (C H ) (C H ) 4 and (C H ) Ar-C H Conclusions Chapter 3 Dimeric Absorption in the Atmosphere 60 A. A. Vigasin 1 Introduction 60 Weakly Bound Species in Planetary Atmospheres 61.1 Jupiter, Saturn, and Titan 61. Mars and Venus 67.3 Earth 7 3 Water Vapor Continuum Absorption Water Complexes and Continuum Absorption About Controversies of Dimeric Hypothesis Concluding Remarks 91 9

4 Chapter 4 Dimers in Earth's and Planetary Atmospheres: The (H O), (N ), N -O, (O ), (O 3 ), (CO ), (H ), and Ar-N Cases Z. Slanina, S. J. Kim, K. Fox, F. Uhlik, and A. Hinchliffe ix Introduction The Water Dimer The (N ), N -O, and (O ) Species The Ozone Dimer (CO ) & Venus (H ) & Jupiter Ar-N & Titan Concluding Remarks Chapter 5 Fullerenes & Other Carbon Aggregates, and the Diffuse Interstellar Bands Z Slanina, L. Adamowicz, J.-P- Franqois, ande. Osawa 1 Introduction The Diffuse Interstellar Bands.1 Highly Unsaturated Hydrocarbons 3 Small Carbon Clusters 4 Cg 0 and C 70 Fullerenes 4.1 Fullerenes in Nature 4. Seminatural Occurrence of Fullerenes 5 Higher Fullerenes 6 Modified Fullerenes 7 Concluding Remarks

5 x Chapter 6 Planetary Atmospheres: The Role of Collision-Induced Absorption 177 L M. Trafton 1 Introduction 177 Historical Background CIA Enhancement of the Greenhouse Effect Voyager Observations of the CIA Rotational- Translational Band of H -He The He/H Ratio The Ortho-Para H Ratio Post-Voyager Results Ground Based Observations of the H Fundamental Band Venus and CIA Night Sky Emission from CO igg 5.3 A Massive Early Atmosphere on Triton? The.15 um N Ice Band and the Atmospheres of Triton and Pluto Extrasolar Planets Chapter 7 Chemical and Optical Properties of Molecular Complexes Using Matrix Isolation Spectroscopy L. Schriver-Mazzuoli 1 Introduction Experimental Techniques.1 Closed-cycle Refrigeration. Sample Preparation.3 Sample Deposition.4 Matrix Properties.5 IR Spectroscopy in Matrices 3 Vibrational Spectroscopy 3.1 Charge Transfer Complexes

6 xi Halogen-Base Complexes Ozone-Base Complexes SO and SO3-Base Complexes Oxygen-Base Complexes Hydrogen-Base Complexes Hydrogen Bonded Complexes Weak and Medium Hydrogen Bonded Complexes Hydrogen Halides Water: Self Association Water: Heteromolecular Complexes Water Ices Alcohols Ammonia, Hydoroxylamine Nitric and Nitrous Acid Carboxylic Acids Proton Transfer Trapping of Two Structural Arrangements of Weak Complexes Infrared Photodissociation of Hydrogen Bonded Complexes 4.1 Hydrogen Bonded Complexes IH...B C > U Conversion C < U Back Conversion 4. Infrared Photoisomerization of the ROH Aggregates (R = CH 3, H) Methanol Dimer Methanol Trimer Water Dimer UV and Visible Photochemistry Case Study: Photodissociation of the O 3 : Br and O 3 : BrCl Complexes in Argon Matrix at 53, 633, and 870 nm 7 30

7 xii Chapter 8 Infrared Spectroscopy of Size-Selected Free and Adsorbed Water Complexes 38 F. Huisken 1 Introduction 38 Experimental 41.1 Principle of Measurements 41. Experimental Details 43 3 Results Free Water Clusters Water Complexes Embedded in Argon Host Clusters Water Complexes Embedded in Helium Host Clusters 3.4 Methanol Attached to Water Host Clusters Discussion 4.1 Assignments 4. Comparison with Calculations 4.3 Solvated Water Complexes 4.4 Correlation between Frequency Shift and Critical Temperature Summary