Astrochem SB Nov2009 WWW

Astrochemistry
Adwin Boogert NASA Herschel Science Center, Caltech, Pasadena, CA
17/Nov/2009
SUNY Stony Brook Astrochemistry Lecture
Contents

What is Astrochemistry? Chemical Reactions in Space Gas Phase neutral and ion reactions Grain surface chemistry Tunneling Mantle growth Ice formation threshold Ice processing Laboratory simulations Thermal processing Energetic processing Observing Interstellar Molecules Gas Phase IR versus radio observations Detected Species
17/Nov/2009
Contents
Observing Interstellar Molecules Solid State Band profiles Polar versus apolar ices; Sublimation Amorphous versus Crystalline ices; Time scales Grain size/shape effects Column densities Molecular Evolution: Dense Clouds Low and High Mass Young Stars Hot Cores+Disks Stars Stellar Death Diffuse Clouds Astrobiology Future: Herschel, ALMA, JWST
17/Nov/2009
Reading
Material covered in this lecture is described at a similar level in
Complex Organic Interstellar Molecules, E. Herbst and E. F. van Dishoeck, ARA&A 2009, 47, 427-480. No need to read sections 2, 3.3, 5.2, 5.3, 6.4-6.6.
For the interested:
More advanced astrochemistry chapters in The Physics and Chemistry of the Interstellar Medium, A. G. G. M. Tielens, ISBN 0521826349. Cambridge, UK: Cambridge University Press, 2005. Astrobiology: An Introduction to Astrobiology, eds. I. Gilmour and M. A. Sephton, ISBN 0521546214. Cambridge, UK: Cambridge University Press, 2003, 2004.
17/Nov/2009
What is Astrochemistry?
Astrochemistry studies molecules anywhere in the universe: how are they formed? how are they destroyed? how complex can they get ? how does molecular composition vary from place to place? use them as tracer of physical conditions (temperature, density)? how are molecules in space related to life as we know it (astrobiology)?
17/Nov/2009
Chemical Reactions in Space

Cosmic Abundances
Key factors in interstellar chemistry:
H He O C N Ne Si Mg S Fe
0.9 0.1 7e-4 3e-4 1e-4 8e-5 3e-5 3e-5 2e-5 4e-6
H2 inert CO CO N2 inert dust dust dust
Abundance H factor 1000 larger than any other
(reactive) elements Away from very strong UV fields: H,N,C,O atoms 'locked up' in H2, N2, CO. Left over atoms determine chemical environment: Reducing environment if H>O Oxidizing environment if H<O
17/Nov/2009
Chemical Reactions in Space

More key factors in interstellar chemistry:
Densities atoms and molecules in interstellar medium extremely low: 1-105
particles/cm3. Compare: earth atmosphere 1019 ultra-high vacuum 108

Therefore chemistry quite unusual compared to earth standards. Rare earth
species (discussed in a few slides) are abundant in the ISM: HCO+ [formyl ion] H3+ [protonated dihydrogen] Types of chemistry:
Gas phase chemistry Grain surface chemistry (freeze out <100 K) Energetic processing ices
17/Nov/2009
Gas Phase Chemical Networks

Despite extreme vacuum conditions,
long time scales allow for complex gas phase chemistry.

Ion-neutral reactions orders of
magnitude faster than neutral-neutral.

Species with ionization potential
<13.6 eV likely photo-ionized (CC+)

Cosmic rays also important ionization
sources
17/Nov/2009
Some Key Gas Phase Reactions

H3+: (recently discovered, see http://h3plus.uiuc.edu) Collides and excites H2, source of UV in dense clouds + + eH2 + CR H2 H2+ + H 2 H3+ + H
HCO+: H3+ + CO HCO+ + H2 H2O:
O + H+ O+ + H O+ + H2 OH+ + H OH+ + H2 H2O+ + H H2O+ + H2 H3O+ + H H3O+ + e- H2O + H
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Grain Surface Chemistry

Many molecules (H2, H2O) much more easily formed on grain surfaces. Freeze out <100 K. Interstellar ice or dirty ice: any frozen volatile, e.g. H2O, H2O mixtures, pure CO. More realistic grain:
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10
Grain Surface Chemistry
Grain surfaces are the watering holes of astrochemistry where species come to meet and mate. (Tielens 2005) Species accreted from gas are chemisorbed or physisorbed on grains, allowing for much longer time to find reaction partner than in gas phase Species move fast over surface, meeting partners many times, allowing for tunneling through activation barriers. e.g. H atom has 50% probability of tunneling through 3400 K barrier. At molecular cloud densities (104-105 cm-3) it takes a few days for an atom to stick to a grain and 5*105 yrs for all gas to deplete on grains, much less than cloud lifetime.
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Ice Mantle Growth

H2O formed by grain surface reactions, CO formed in gas and inertly condenses
on grains. Grain mantle thickness: Mass growth rate: dm/dt=S**a2*n*<v>*<m> Radius growth rate: da/dt=(dm/dt)/(4**a2*) da/dt=S*n*<v>*<m>/(4*) Mantle thickness independent of grain radius Dense clouds can have mantles as thick as 0.1 um, and in deeply embedded protostars even more. Mantle thicker than most grain cores according to MRN grain size distribution n(a)~a-3.5, amin=0.005 m, amax=0.25 m
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Ice Mantle Growth

Due to grain temperature and interstellar radiation field ices form only if visual extinction
(AV) large enough: the ice formation threshold Taurus cloud: H2O ices absent below visual extinction AV~3 and CO ices below AV~7. Difference due to lower Tsub of CO. Variation between clouds due to different temperature/radiation field H2O CO
Extinction (AV)
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Simulating Interstellar Ices

Chemical processes occurring in
space can be simulated in laboratory at low T (10 K) and low pressure. Thin films of ice condensed on a surface and absorption or reflection spectrum taken. Temperature and irradiation by UV light or energetic particles of ice sample can be controlled. Astrophysical laboratories: Leiden, Catania, NASA Ames/Goddard, Paris
Gerakines et al. A&A 357, 793 (2000)
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Thermal Processing of Ices

New molecules easily produced by heating acid/base mixtures.
Example shown H2O/NH3/HNCO=120/10/1 at 15, 52, 122 K NH3+HNCO -->NH4+ + OCN NH4+ and OCN- have spectral characteristics that fit interstellar 4.62 and 6.85 m bands. Relative intensities not in agreement with observations, however, when requiring charge balance; further study needed. Van Broekhuizen et al., A&A 415, 425 (2004)
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Energetic Processing of Ices

415, 425-436 (2004)
Chemical processing of ices by UV photons and cosmic rays can be simulated Top figure shows H2O/CO/NH3 ice mixture after photo-processing with hard UV photons Bottom figure shows similar spectra compared to a YSO. Heating after irradiation can explain the 6.85 m band. Long exposure to photons or particles can form very complex molecules, incl. Amino acids and PAHs. Relevance to interstellar medium is hard to prove. See slides on diffuse medium
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Observing Gas Phase Molecules

Molecules detected (mostly) by vibrational and rotational transitions, at infrared and radio wavelengths. Electronic transitions occur at X-ray/UV wavelengths extinction-limited
H2O vibration modes

symmetric stretch v1 bend v2 asymmetric stretch v1
H2O rotation modes

rotation axis A rotation axis B rotation axis C
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Observing Gas Phase Molecules

Ro-vibrational transition rules lead to characteristic P and R branch spectrum, if there is permanent (e.g. CO) or induced (e.g. CH4) dipole moment. N2 and O2 cannot be observed this way. Example CO fundamental (J=1, v=1): Pure rotational lines occur mostly in the far-IR/submm for species with permament dipole moments (e.g. CO, but not CH4)
922 GHz 807 GHz 691 GHz 576 GHz 461 GHz 231 GHz 346 GHz 115 GHz
Note that in solid state, no rotations allowed, leading to one broad vibrational spectrum
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Observing Gas Phase Molecules: Inventory

129 gas phase molecules currently detected in space (123 listed here)
http://www.cv.nrao.edu/~awootten/allmols.html
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Observing Solid State Molecules

H2O ice has many broad absorption bands: Symmetric stretch Asymmetric stretch Bending mode Libration mode Combination modes Lattice mode etc...
Width, position and shape determined by solid state (dipole) interactions band profile powerful diagnostic of ice environment and structure
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Ice Band Profiles Polar vs Apolar Ices

Molecular dipole moment determines physical and spectral characteristics. Compare solid H2O and CO: Sublimation temperature much higher for H2O (90 K vs. 18 K in space) Bands much broader for H2O H2O/CO mixtures: distinct polar and apolar ices with different H2O/CO ratios that can spectroscopically be distinguished and sublimate at different T. Highly relevant for icy bodies (e.g. comets) as well, as dipole moment determines outgassing behaviour. 'Pockets' of apolar CO may result in sudden sublimation.
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CO band consists of 3 components, explained by laboratory simulations as originating from CO in 3 distinct mixtures:
'polar' H2O:CO
'apolar' CO2:CO
'apolar' pure CO
(Boogert, Hogerheijde & Blake, ApJ 568,761, 2002)
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Indeed, CO ice profiles vary dramatically in different lines of sight, as apolar component highly volatile. 'Older' YSOs have less apolar CO
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Ice Band Profiles Amorphous vs. Crystalline

Interstellar H2O ices formed in amorphous phase, as evidenced by prominent 'blue' wing. Crystallization by protostellar heat. [long wavelength wing originates from scattering on large grains and NH3:H2O complexes] Crystallization temperature ~120 K in laboratory, but ~70 K in space due to longer time scales. [Time scale ~exp(Ebarrier/T) (~1 hour in lab, 105 yr in space). For same reason sublimation temperature in lab (~180 K) higher than in space (~90 K)].
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Ice Band Profiles Grain Shape and Size Effects

Laboratory and interstellar absorption spectra cannot always be directly compared: Scattering on large (micron sized) grains leads to 3 m red wing (often observed) Surface modes in small grains may lead to large absorption profile variations: For ice refractive index m=n+ik, absorption cross section ellipsoidal grain proportional to (Mie theory) (2nk/L2)/[(1/L-1+n2-k2)2+(2nk)2] Resonance for sphere (L=1/3) occurs at k2-n2=2, so at large k (=strong transitions) Important for pure CO, but not for CO diluted in H2O and also not for 13CO.
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Ice Column Densities and Abundances

Ice column densities: N=peak*FWHM/Alab Alab integrated band strength measured in laboratory A[H2O 3 m]=6.2x10-16cm/mol. Order of magnitude in quiescent dense clouds: N(H2O-ice)=1018 cm-2 For reference: this is ice layer of 0.3 m at 1 g/cm3 in laboratory, but.... Ice abundance: X(H2O-ice)=N(H2O-ice)/NH~10-4 This is comparable to X(CO-gas)
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Ice Inventory
'Typical' abundances w.r.t. H2O ice
CO CO2 CH4
CH3OH HCOOH [NH3] H2CO [HCOO-] OCS [SO2] [NH4+] [OCN-]
few-50% 15-35% 2-4%

<8, 30% 3-8% <10, 40% (?) <2, 7% 0.3% <0.05, 0.2% <=3% 3-12% <0.2, 7%
Note far fewer ices detected than gas phase species. This is because ices can only be detected by absorption spectroscopy.
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Molecular Evolution
Next slides molecular evolution: Dense Clouds Young Stars Hot Cores/Disks Stars Stellar Death Diffuse Clouds Astrobiology
Not independent environments. Cycling of matter is key.
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Molecular Evolution: Diffuse vs. Dense Medium

Hubble telescope image of M51 shows massive young stars (red) 'normal' stars (white) molecular clouds (black) diffuse clouds in between clouds 'processed' by UV photons massive stars very similar to our own Galaxy Cycling between environments as spiral density wave passes
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Molecular Evolution: Diffuse vs. DenseM51 highlighting Medium CO J=1-0 image

giant molecular clouds. [Obtained with CARMA array in Owens Valley by Jin Koda]
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Molecular Evolution: Dense Core

Background star extinction NH4+
H2O H2O
silicates Wavelength Molecules in core freeze out at sublimation temperature of molecule. H2O T=90 K CO T=16 K
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Molecular Evolution: Dense Core

CO sublimation temperature ~16 K In densest part of core, most CO freezes out N2 and H2 lower sublimation temperature (<13 K) cosmic rays penetrate deep in core, ionizing H2, forming N2H+
H2 + CR H2+ + eH2+ + H2 H3+ + H H3+ + N2 N2H+ + H2

N2H+ observable at sub-mm frequencies (e.g. Herschel) better dense cloud tracer than CO
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Molecular Evolution: Young Stars
Deep ice bands observed toward young stars. As star ages, ices heated: crystallization and sublimation (most volatile species, e.g. CO) first.
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Observational evidence for thermal processing of ices near YSOs:
Solid 13CO2 band profile varies toward different protostars
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34


Solid 13CO2 band profile varies toward different protostars and laboratory simulated spectra show this is due to CO2:H2O mixture progressively heated by young star (Boogert et al. 2000; Gerakines et al. 1999)
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Solid 13CO2 band profile varies toward different protostars and laboratory simulated spectra show this is due to CO2:H2O mixture progressively heated by young star (Boogert et al. 2000; Gerakines et al. 1999) H2O crystallization (Smith et al. 1989) gas/solid ratio increases (van Dishoeck et al. 1997) Detailed modelling gas phase mmwave observations (van der Tak et al. 2000) Little evidence for energetic processing of ices, however......
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Molecular Evolution: Hot Cores

......., but in immediate vicinity of YSO ices evaporate, and warm gas directly observable at submm/radio wavelengths in rotational transitions. (sub)millimeter-wave gas phase measurements orders of magnitude more sensitive to abundances than IR ice observations Regions called hot cores for massive young stars and corinos for low mass stars.
Cazaux et al. 2004
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Have to be able to separate flowers from the weeds Formic acid Formic acid Methyl formate Dimethyl ether
SGR B2(N), ALMA Band 6 mixer at SMT A. Wootten, Science with ALMA Madrid 2006.
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Herschel/HIFI: 480-1916 GHz (625-157 m). Resolving Power up to 10 million, or <0.1 km/s
CH3OH gas cell measurement using HIFI (Teyssier et al. 2005)
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Molecules are (Nearly) Everywhere

even on the Sun T>5000 K, most molecules dissociate Lower T, molecules quite easily formed, as demonstrated by H2O detection in sun spots (T~3000 K)
~13 um
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Molecular Evolution: Stellar Death

Stars at end burning phase expel massive shells of
matter, enriching ISM with new elements and dust

Effect on chemistry strongly depends on stellar
mass, and episode of explosion.
Cas A, Spitzer
Some form oxygen-rich dust (silicates), others
SN 1987A, HST
graphitic dust (and PAHs).

Supernovae vaporize environment,
destroying or modifying dust (graphite diamond).

Molecules (CO and SiO) formed in ejecta Produce cosmic rays
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Molecular Evolution: Diffuse Medium, Mystery 1
PAHs
Diffuse Interstellar Bands discovered in 1922 in optical spectra of diffuse medium. Over 200 bands detected. Probably a large gas phase species Polycyclic Aromatic Hydrocarbons possible spherical C60, Buckminster Fullerenes, Buckyballs problem not solved...: 1 DIB, 1 carrier?
Buckyball 17/Nov/2009
42

Another enigmatic diffuse
medium feature.... the 3.4 um absorption band toward the Galactic Center).
Triple peaks due to
-CH-CH3-CH2-
hydrocarbons (-CH, -CH2, CH3), but what kind of hydrocarbon?
Pendleton et al. 1994, Adamson et al. 1998, Chiar et al. 1998, Chiar et al. 2000
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Bacteria? Apples?
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Greenberg et al. ApJ 455, L177 (1995): launched processed ice sample in earth orbit exposing directly to solar radiation (EUREKA experiment). Yellow stuff turned brown: highly carbonaceous residue, also including PAH.
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Little evidence production by UV/CR bombardment of ices: band not polarized as opposed to silicates/ices: not in processed mantle but separate grains 3.4 um band observed in dense clouds, but not triple peaked. Likely NH3.H2O hydrate. Due to Low infrared sensitivity? Better observe sublimated species (more sensitive) formed in evolved star envelopes, and injected in ISM?
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Molecular Evolution: Astrobiology

Do molecules formed in interstellar medium have anything to do with
formation of life? This is topic of astrobiology. Amino acids building blocks of most complex molecules in living organisms...protein. It has been produced in laboratory by heavy processing interstellar ice analog. Also, chirality of amino acids in protein is left-handed. May have been caused by nearby massive star producing circularly polarized light
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Future of Astrochemistry is Bright....
Atacama Large MM Array

Herschel Space Observatory James Webb Space Telescope
.plus a lot more 17/Nov/2009
48

Astrochem SB Nov2009 WWW

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Astrochemistry

Adwin Boogert NASA Herschel Science Center, Caltech, Pasadena, CA

SUNY Stony Brook Astrochemistry Lecture

SUNY Stony Brook Astrochemistry Lecture

SUNY Stony Brook Astrochemistry Lecture

For the interested:

SUNY Stony Brook Astrochemistry Lecture

SUNY Stony Brook Astrochemistry Lecture

Chemical Reactions in Space

H2 inert CO CO N2 inert dust dust dust

Abundance H factor 1000 larger than any other

SUNY Stony Brook Astrochemistry Lecture

Chemical Reactions in Space

particles/cm3. Compare: earth atmosphere 1019 ultra-high vacuum 108

SUNY Stony Brook Astrochemistry Lecture

Gas Phase Chemical Networks

long time scales allow for complex gas phase chemistry.

magnitude faster than neutral-neutral.

<13.6 eV likely photo-ionized (CC+)

SUNY Stony Brook Astrochemistry Lecture

Some Key Gas Phase Reactions

O + H+ O+ + H O+ + H2 OH+ + H OH+ + H2 H2O+ + H H2O+ + H2 H3O+ + H H3O+ + e- H2O + H

SUNY Stony Brook Astrochemistry Lecture

Grain Surface Chemistry

SUNY Stony Brook Astrochemistry Lecture

Grain Surface Chemistry

SUNY Stony Brook Astrochemistry Lecture

Ice Mantle Growth

SUNY Stony Brook Astrochemistry Lecture

Ice Mantle Growth

SUNY Stony Brook Astrochemistry Lecture

Simulating Interstellar Ices

Gerakines et al. A&A 357, 793 (2000)

SUNY Stony Brook Astrochemistry Lecture

Thermal Processing of Ices

SUNY Stony Brook Astrochemistry Lecture

Energetic Processing of Ices

SUNY Stony Brook Astrochemistry Lecture

Observing Gas Phase Molecules

H2O vibration modes

H2O rotation modes

SUNY Stony Brook Astrochemistry Lecture

Observing Gas Phase Molecules

SUNY Stony Brook Astrochemistry Lecture

Observing Gas Phase Molecules: Inventory

SUNY Stony Brook Astrochemistry Lecture

Observing Solid State Molecules

SUNY Stony Brook Astrochemistry Lecture

Ice Band Profiles Polar vs Apolar Ices

SUNY Stony Brook Astrochemistry Lecture

Ice Band Profiles Polar vs Apolar Ices

(Boogert, Hogerheijde & Blake, ApJ 568,761, 2002)

SUNY Stony Brook Astrochemistry Lecture

Ice Band Profiles Polar vs Apolar Ices

SUNY Stony Brook Astrochemistry Lecture

Ice Band Profiles Amorphous vs. Crystalline

SUNY Stony Brook Astrochemistry Lecture

Ice Band Profiles Grain Shape and Size Effects

SUNY Stony Brook Astrochemistry Lecture

Ice Column Densities and Abundances

SUNY Stony Brook Astrochemistry Lecture

few-50% 15-35% 2-4%