Laboratory Studies of Organic Chemistry in Space A. Ciaravella Palermo, 2014 March 26 InterStellar Medium (ISM) overview ISM composition Dust and Ice Mantles : synthesis of complex molecules Laboratory Astrochemistry: main results Space vs Laboratory conditions IR Spectroscopy (Ices) An experiment step by step Synthesis of organic compounds on the origin of life
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Laboratory Studies of Organic Chemistry in Space A. Ciaravella Palermo, 2014 March 26 InterStellar Medium (ISM) overview ISM composition Dust and.
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Laboratory Studies of Organic Chemistry in SpaceA. Ciaravella
Palermo, 2014 March 26
InterStellar Medium (ISM) overview ISM composition Dust and Ice Mantles : synthesis of complex moleculesLaboratory Astrochemistry: main results Space vs Laboratory conditions IR Spectroscopy (Ices) An experiment step by step Synthesis of organic compounds on the origin of life
InterStellar Medium (ISM)
The ISM: ● mostly gas and dust existing over a wide range of physical conditions
● dust is 1% in mass
● half of the ISM mass in our Galaxy is composed by molecule
● processed by the radiation field from stars and cosmic rays
● Can be devided in 5 components:“coronal” gas warm intercloud medium HII regionsneutral hydrogen (HI) cloudsand complexes of giant molecular clouds (GMCs)
ISM: Hot and Warm Gas
Hot or Coronal gas T ≥ 106 k n ≤ 0.5 cm-3
Hot gases ejected in stellar explosions and winds Observed as ar-UV absorption lines of highly ionized atoms soft X-ray background VELA
(0.1 - 2.4 keV), ROSAT
Warm gas T ≤ 104 k 0.1 ≤ n ≤ 1 cm-3
The source in not entirely clear Can be neutral or ionized Observed as neutral − n ≈ 1 cm-3 − emission features in HIIonized ( UV radiation) − n ≈ 0.1 cm-3 − HII
Orion nebulaHubble Space Telescope
Neutral Hydrogen Clouds
Almost half of the ISM T < 102 K n ≈ 50 cm-3
Observed in neutral HI 21 cm line
Excellent tracers of spiral structure
Molecular Clouds
Large variety Diffuse, Giant, Dark, Dense cores T ≤ 10 − 50 K n 10≅ 2 – 104 cm-3
sizes 20-200 pc masses 103-107 M
mean density 102 cm-3
In cores (~1pc) n ~104 cm-3
Sites of chemical and dynamical activity leading to star formation H2 is the dominant molecule but CO is used to map the clouds
A Multi-Wavelenght View of the Milky Way
Visible
HI 21cm
CO 115GHz
H2
X-ray
Dust extinction Dark regions
ISM Composition
Neutral Atoms: mainly H and He, with signicant amounts of C, N, O
Ions: mainly H+ and cations of other abundant elements. Cations are the dominating ions in ISM
Electrons: from ionization. Free electrons are signicantly abundant.
Small Size Molecules: the most abundant are H2 and CO, but
other small size are present, mainly in molecular clouds.
Larger Molecules: mainly, polycyclic aromatic hydrocarbons PAH have been found in many places in galaxies.
Dust Particles: small particles 0.01 − 1 μm Composition Si, Fe, C, and O Play a crucial role in the formation of molecules
Molecular Clouds: the richest in molecules
Where and in which conditions complex molecules can be produced?
1) Medium complexity molecules e. g. CO , NH3, H2O, HCnN (up to n=13)
2) Polycyclic Aromatic Hydrocarbons (PAH) , C C multiple bonds
3) Large partly H saturated molecules( with no C C multiple bonds & > 3 H)
Which are the formation routes?
3-body no working in gas phase.
2-body efficient in gas phase for 1) and 2)
No gas phase routes for 3) !!!
Need for a heterogeneous chemistry
Chemistry in Dust Grain Mantles I
Dense (≥104 cm-3) and cold (10 – 20 K) regions
t ≤ 105 yr
Freeze-out time t ≈ 109/n [yr]
Diffuse ISM n ≈ 102 t ≈ 107 yr too long!!
Ice Mantles
Visible C18O N2H+
Evidence for freeze out appear as emission holes in the maps of some molecules
Dust grains have icy mantles
Chemistry in Dust Grain Mantles II
Mobilty of particles is necessary for chemical reactions:✓quantum tunneling, τq =4h/ΔE for H
✓thermal hopping, τh=ν-1exp(TB/T)reactions
diffusion
desorption
H2O
CH3OH
CO
NH3
CO2
Silicatecore
adsorption
CH3OH
CH4
C
O
H
Adsorption or sticking efficiency is high for dust grains.
Desorption occurs continuously: ✗ Micro exothermic reaction liberates molecule from surface; ✗Macro explosive liberation of molecules by mantle destruction by energetic photons or cosmic rays;
✗ Violent collective destruction of grains by shock waves
Feeding the ISM From Prestellar through the collapsing envelope into a planetary disk
Laboratory Astrochemistry: ICES
1979 - UV irradiation ✓Hydrogen lamp 1216 Å 10.6 eV ✓T higher than today exp ✓6eV min E for breaking typical molecular bonds
~ 1983 - Particle bombardment
effects of sputtering and ionchemistry
mediated by the solar wind and cosmic rays Energies Few keV to hundred MeV
Ion beam
Sample
after Zombec handbook
The brightest UV line
Many of the observed molecules have been produced in laboratory
Laboratory Astrochemistry: Results
UV CH3OH (Öberg et al 2009) UV NH3:CO
(Grim et al 1989)
46 MeV ions H2O:NH3:CO(Pilling et al. 2010)
A Typical Laboratory Setup
IR
Radiation Source
Mass S
pect,
Gas Inlet
1 − A gas is deposited on a cold (≤ 15 K) InfraRed transparent substrate
2 − The ice is then irradiated
3 − Ice evolution is followed by means of IR spectroscopy (mostly transmission)
4 − After irradiation the substrate is heated at a rate of 1-2 K min-1 or slower
5 − The ice desorbs and the desorbed species are detected by the Mass Spectrometer
6 − Refractory residue on the substrate
LIFE(Light Irradiation Facility for Exochemistry)
Pumping SystemGas Line
Control System
Cold Finger
IR Spectrometer
Needle Valve Gas Inlet
Mass Spectrometer
UV Source ( HI Lyα )
Laboratory vs ISM Conditions: I
Temperature 4 - 10 K or higher
Chamber pressure:
early exp. ~ 10-7 mbar
today exp. ~ 10-10 mbar
~ 5 × 10-11 mbar
How many part. cm-3 in the chamber?
At sea level ~1bar and Standard Temperature and Pressure (STP) we have
In the best case the density inside the chamber is: ≈ 1.3 × 106 particle cm-3 !!!
Laboratory vs ISM Conditions: II
!! MUCH MORE dense (> 104 times) than the average density in ISM
This value is closer to:
✔Dense cores in molecular clouds (where ices form!)
✔Regions of stellar formations
In the best case the density inside the chamber is: ≈ 1.3 × 106 particle cm-3 !!!
ISM gas is mainly H2 and CO
CO /H2 ≈ 10-6 − 10-4 Diffuse to Dense gas
Laboratory Vacuum Composition
H2
CO CO2
H2O
2 × 10-9 mbar
5.3 × 107 part. cm-3
1.5 × 10-10 mbar
4 × 106 part. cm-3
ISM CO /H2 ≈ 10-6 − 10-4
Laboratory vs ISM Conditions: II cont
Lab CO /H2 ≈ 0.4 − 0.5
H2O !!!
As in the ISM particles in the chamber stick to the ice.
Sticking coefficient S measures the capability of a given species to stick to a surface
Laboratory vs ISM Conditions: III
S = f (Surf. Cov, T, F, ….) 0 ≤ S ≤ 1
The time required to accrete
Assuming S=1
~ 28 hours !!
Coarse vacuum conditions high deposition of H2O on top of the ice
Laboratory vs ISM Conditions: III cont
Radiation fluxes in the lab are orders of magnitude larger than in the space ✖ even if compatible with stellar emission ✖ not much with the fluxes inside the clouds
UV
X
Molecular clouds are stable over time > 3 × 107 yr
Laboratory chemistry is quick! ✔ Irradiation times range from min to several hours ✔The same absorbed energy/photon could take several yr ( or much more !!) in space UV space 6< F<2000 eV 108 cm-2 s-1 Lab 1015 cm-2 s-1
103 yr 1 h
Molecular InfraRed Spectra
InfraRed spectra originate from molecules vibrational-rotational modes
105 104 103 102cm-1 101
λ = 2.5 × 10-3 cm = 400 cm-1
10-5 10-4 10-3 10-2cm 10-1
λ = 2.5 × 10-4 cm = 4000 cm-1
Ultraviolet Visible Near InfraRed Far Infrared Microwaves infrared
Near−IR: Overtone or Harmonic vibrationsMid−IR: Fundamental vibrationsFar−IR: Rotational Spectroscopy
ICES
Transmittance
Absorbance
InfraRed Spectra
Iλ(0) Iλ
IR Source
IR Detector
molecule & line dependent
d
Absorption/Transmission
coupling of a dipole vibration with the electric field of the infrared radiation
Optical depth
Molecular Vibrational Spectra
Symmetrical Strecthing
Wagging
TwistingAsymmetrical
Strecthing
RockingScissoring
Not all the molecules are IR active: H2, N2 are IR inactive CO2 linear molecule is IR inactive for symmetric stretch of the O atoms
Change in the dipole moment molecular IR band
CH2
InfraRed Spectra: II
Tra
smit
tanc
e %
Wavenumber (cm-1)
Functional Groups Molecular Fingerprints
The absorption due to a particular dipole oscillation is generally not affected greatly by other atoms present in the molecule.
The absorption occurs at ~ the same frequency for all bonds in different molecules.
Bonds with H (vs C, O) higher energies
InfraRed Spectra: III
Absorption of C = O occurs always 1680 − 1750 cm-1
O − H “ “ “ 3400 − 3650 cm-1
C = C “ “ “ 1640 − 1680 cm-1
InfraRed Spectra: cont
The Column Density
The ice tickness
Avogadro number
molecular mass
species density
X-ray Irradiation of Ices
Why X-ray Irradiation ?
Almost all stars are X-ray emitters
Emission varies with age
Young stars X-rays > EUV & vacuum UV
X-rays penetrate deeply in circumstellar regions inhibited to EUV and UV
after Gudel 2003
X-ray irradiation of ICEs is a new research field
after Ribas et al. 2005
X-ray Interaction with the IceUV HI Lyα 10.9 eV interacts with molecular bonds
X-rays photons interact with the atoms of the molecules
KE = hν – BE Auger KE = EA- EB - EC
A=1s
B=2p1/2
C=2p3/2
Interaction of ices with X-rays is a multistep process Ionization of the atoms in the molecule Production of secondary e- which in turn interact with the medium
Z BE (eV)1s 2p1/2 2p3/2
8 O 532 24 7
2 e- 18 & 501 eV
ph 550 eV = 18 eV = 501 eV
hν < BE atom into an excited state accompained by single electron emission
X-ray Irradiation of Ice
1) Irradiation of simple ices: CO, CO2, H2O, CH3OH study the products their dependence from physical parameter
≥ 75% contains CarbonThe interstellar chemistry is
carbon-dominated
Organic Molecules & Origin of Life on Earth
Our Solar System was born 4.6 × 109 yr
Life started on Earth3.6 × 109
3.8 × 109 End of impactsOnly 200 million yr !
Meteorites, comets etc etc bombardment
3.55 × 109 yr old fossilized microorganisms (< 10 μm)from the Barberton Greenstone Belt (South Africa).
CONDITIONS NOT CONDUCIVE TO LIFE
1953: Miller Experiment
… if (& oh what a big if) we could conceive in some warm little pond with all sorts of ammonia & phosphoric salts,—light, heat, electricity……a protein compound was chemically
formed ….(Charles Darwin, 1 Feb 1871, letter to J.D. Hooker)
Earth atmosphere composition(N2, CO, CO2 H2O) …… too rich of O
CH4, NH3, H2O, H2
Amino Acids in Space ?
To date amino acids have not been detected in the Interstellar Medium.