Editorial
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Introduction: Astrochemistry
A strochemistry is the study of the rich and diverse
chemistry that occurs throughout the universe. The field
of astrochemistry is truly interdisciplinary and involves a variety
of scientists, including those who study relevant physical and
chemical processes in the laboratory and on the computer,
those who observe molecular spectra through large telescopes
in assorted regions of the spectrum, and those who simulate the
chemistry of individual regions with large kinetic models
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somewhat akin to those used in combustion studies.
Much if not most of the visible matter in the universe is
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divided into galaxies, which contain up to billions of stars along
with interstellar matter. The mass is divided among the many
elements, with hydrogen the most abundant, helium lower by a
factor of 10 by number, and the chemically important elements
C, N, and O lower by a factor of 103−4. The interstellar material
resides mainly in the form of clouds, consisting of gas and tiny
dust particles. These clouds are the only known birthplaces of
stars and planets. The clouds, which can extend up to 100 pc,
or 300 light years, in size, range from diffuse objects, through
which the light of background stars can be seen, to very dense
objects, which extinguish all background visible and ultraviolet
light, but can be studied at longer wavelengths from the
infrared to the radio spectral range.
The field of astrochemistry started to achieve its current
status in 1968, when ammonia was first detected by Townes
and co-workers toward the center of our galaxy via its inversion
transitions. Since that time, almost 200 different gas-phase
molecules have been detected in the so-called interstellar
medium, mainly in dense interstellar clouds via rotational
emission spectroscopy in the millimeter and submillimeter
portions of the spectrum. The molecules detected by this
technique, which range in size up to 13 atoms, are
overwhelmingly organic in nature. Not only do interstellar
spectra tell us what molecules are present and how abundant
they are, but they also tell us the physical conditions of the
environment in which they are formed.
Despite difficulties caused by water vapor absorption in our
own atmosphere, the infrared region of the spectrum has been
used to study the vibrations of interstellar molecules both in
absorption, with either background stars or protostars, which
are stars in the act of formation, as lamps, and in emission.
Infrared absorption studies have been used to probe both the
interstellar gas and the molecules that comprise interstellar dust
particles, while emission studies have detected very large
molecules; namely, polycyclic aromatic hydrocarbons (PAHs)
and the fullerenes C60+, C60, and C70. Unlike the gas phase, the
molecules comprising dust particles are not exotic: these
particles are known to have cores of silicates or amorphous
carbon and, in dense cold regions, to have mantles of ices,
mainly consisting of water, CO, CO2, and methanol.
The history of interstellar molecules begins with generations
of old stars, which emit gas and dust either explosively, as in
supernovae, or more gently, in expanding stellar envelopes. The
atoms and dust particles collect under the influence of gravity
into diffuse clouds, of temperature 50−100 K and gas density
© 2013 American Chemical Society
10−102 cm−3, where interstellar chemistry begins. Although
this chemistry is not as rich as detected in dense clouds, some
molecules do exist, the most abundant of which is molecular
hydrogen, which is roughly of equal abundance to atomic
hydrogen.
Further gravitational contraction leads to dense clouds, of
average gas density 103 cm−3, where star formation begins.
Dense clouds come in several varieties and are quite
heterogeneous. The gas-phase chemistry of low-mass star
formation begins in “cold” prestellar cores, where the
temperature can be as low as 5−10 K and the gas density is
104 cm−3. Under these conditions, only binary reactions
without activation energy occur appreciably; such constraints
are met mainly by exothermic ion-neutral reactions. The
ionization stems mainly from collisions with cosmic rays, which
are high-energy nuclei, whizzing around at a speed near that of
light. The chemistry leads to an assortment of molecular
species, including relatively common terrestrial molecules such
as CO, which is the second most abundant molecule in the gas,
with a concentration of 10−4 that of H2. But, in addition, a
variety of exotic species are produced, including radicals (e.g.,
C6H), molecular cations (e.g., H3+, HCO+), anions (e.g.,
C6H−), metastable isomers (e.g., HNC, H2CCCC), and
unsaturated long carbon chains (e.g., HC11N). The predicted
concentrations of these and other species obtained from
chemical simulations involving thousands of chemical reactions
are often quite accurate by astronomical standards; viz., within a
factor of 3 of values obtained from observation of spectra.
Chemical simulations are also used to predict concentrations of
molecules that comprise the ice mantles of cold dust grains;
these species are, with the notable exception of CO, formed by
chemical processes rather than simple accretion from the gas.
The initial collapse of prestellar cores leading to low-mass
star formation is isothermal in nature because of cooling caused
by the emission of radiation from collisionally excited atoms
and molecules. Over time, a dense central condensation builds
up, out of which radiation cannot escape. As the continuing
collapse starts to heat up the central condensation and material
collapsing toward it, the region now becomes what is known as
a protostar. When the collapsing gas and dust reach
temperatures of 100−300 K and become a “hot core”, the
chemistry changes dramatically; many common organic species
can now be observed, including alcohols, esters, acids,
aldehydes, etc. In addition, violent shocks blow out material
and, perhaps most importantly, disks of gas and dust begin to
form and rotate around the young protostar. In the disks, the
dust particles start to coalesce into macroscopic bodies,
eventually to become comets, meteors, and even extrasolar
planets. At the same time, much of the natal cloud is blown
away, and what is left is a young star surrounded by a dense
protoplanetary disk, which can eventually evolve into a
planetary system. Our understanding of the formation of
Special Issue: 2013 Astrochemistry
Published: December 11, 2013
8707 dx.doi.org/10.1021/cr400579y | Chem. Rev. 2013, 113, 8707−8709
Chemical Reviews
high-mass stars is very much less advanced than that of the low-
mass variety for a number of reasons, including the fact that
none of these relatively rare stars is very close to the earth, and
they evolve through their assorted evolutionary stages much
more quickly. There are many other regions in the universe
with unusual chemistry, all of which are studied by astro-
chemists.
In this thematic issue, we present 13 papers on assorted
topics of current importance in astrochemistry. These papers
can be divided, at least partially, into the following ordered
topics: basic interstellar chemistry, databases, and modeling;
molecules as probes; chemical and physical processes of
relevance to astrochemistry; chemical simulations of evolu-
tionary stages in star formation; and weathering of solar system
bodies.
The thematic issue begins with an article by Marcelino
Agúndez and Valentine Wakelam on the gas-phase chemistry of
cold cores in dark interstellar clouds. The chemistry, dominated
by ion-neutral reactions, was one of the first to be studied, and
dark cloud cores are perhaps the best studied regions of the
interstellar medium. The article ends with a lengthy treatment
of the basic chemistry that occurs in the gas of dark clouds, and
the extent of the agreement with observation.
The chemistry discussed in the article by Agúndez and
Wakelam leads naturally into the following article by Takeshi
Oka, which focuses on the basic molecule H3+, its spectroscopy,
its interstellar chemistry, and its use as a probe. One of the
main uses of this species is to constrain the ionization rate
caused by cosmic rays in these diverse regions.
The precursor of much of the gas-phase chemistry in the
interstellar medium is molecular hydrogen, yet under
interstellar conditions, this molecule can only be formed
appreciably on the surfaces of dust particles by association of
two hydrogen atoms. Although astrochemists have long
estimated the rate of the interstellar formation of H2, detailed
laboratory studies are more recent. Gianfranco Vidali, who,
along with colleagues, pioneered the experimental study of H2
formation on surfaces of interstellar relevance, discusses in
detail experiments and their interpretation on the surface
formation of H2.
One of the results of our increased understanding of
interstellar chemistry involving dust grains is the distinction
now made between surface chemistry on bare grains and
chemistry that occurs both on and in ice mantles. Tetsuya
Hama and Naoki Watanabe, leaders in the field of ice chemistry
of relevance to the interstellar medium, discuss a number of
aspects of this chemistry from the experimental point of view.
In particular, they discuss the following processesadsorption,
desorption, diffusion, tunneling reactions, and nuclear spin
conversion on amorphous solid water, and they relate their
experimental work to what occurs in the cold interstellar
medium. Among the molecular syntheses featured in the article
are the formation of ices of water, methanol, and carbon
dioxide. Deuterium enrichment on ice, especially of form-
aldehyde and methanol, is also a key topic.
In gas-grain simulations of interstellar regions, the chemistry
in both the gas and on grains is typically treated by kinetic rate
equations. Yet there are problems with this basic treatment,
especially as regards grain surfaces and grain mantle chemistry,
where the small number of reactive species, such as hydrogen
atoms on individual grains, and the need to consider irregular
surfaces are more accurately treated by stochastic methods. A
leader in this field, Herma Cuppen, along with L. Karssemeijer
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Editorial
and T. Lamberts, explores the use of kinetic Monte Carlo
(KMC) stochastic methods and their relation to astrochemis-
try.
In the next article, Wolf Geppert and Mats Larsson begin
with a very useful introduction to gas-phase ion-neutral and
ion-electron chemistry throughout the interstellar medium and
the outer Solar System, and then they discuss experimental
measurements and results for dissociative recombination, ion-
neutral, and even ion−ion reactions.
The role of gas-phase collisions in the interstellar medium is
not limited to reactions; inelastic nonreactive collisions are also
of great importance because they help to determine internal
state distributions in the frequent case in which thermal
equilibrium does not adequately describe the system. Evelyne
Roueff and François Lique discuss recent advances in the
theory of and experiments concerning molecular excitation in
the ISM via collisions as well as radiation and chemical
processes. The authors speculate that interstellar chemistry will
eventually incorporate some of the state-to-state collisions/
reactions now studied in the laboratory and theoretically.
The next four papers discuss the chemistry that occurs
during star formation, and how it differs from the ion−
molecule, ion−electron chemistry that dominates the gas phase
of cold interstellar clouds. Robin Garrod and Susanna Widicus
Weaver start off this section of the thematic issue with a review
of chemical simulations of hot core chemistry using gas−grain
networks of chemical reactions. Much of what is detected in the
gas phase is thought to derive from radical−radical reactions
that occur on warming dust particles, on which molecules
heavier than hydrogen can diffuse sufficiently to react, and the
products can eventually sublime into the gas as the temperature
continues to rise. The story is continued in the article by Yuri
Aikawa, who emphasizes the dynamics of the physical collapse
from cold core to protoplanetary disk for low-mass star systems
and discusses a variety of hydrodynamic treatments. With
higher dimensional models, a disk starts to form, although the
calculations have so far not been extended sufficiently long to
lead to the formation of a true protoplanetary disk.
During the early stages of collapse, when the temperature has
risen from 10 K to perhaps 30 K, a second phase of ion−
molecule chemistry occurs, as discussed by Nami Sakai and
Satoshi Yamamoto, who label the phenomenon “warm carbon-
chain chemistry”. The chemistry starts when volatile hydro-
carbons such as methane sublime and act as precursors to a new
round of gaseous chemistry that leads, once again, to
unsaturated species known as “carbon chains”.
The chemistry of protoplanetary disks is reviewed by
Thomas Henning and Dmitry Semenov. Chemical simulations
normally assume a fixed physical model, in which the density
and temperature are functions of height from the midplane of
the disk as well as the distance from the central star. The
chemistry in the inner disk, where temperatures can range up to
5000 K, is quite different from the chemistry in the cool outer
disk, where chemical simulations suggest that the chemistry can
be divided into three regions depending upon height.
Protoplanetary disks are small, but the spectra of nearby disks
will be resolved spatially by the Atacama Large Millimeter/
Submillimeter Array (ALMA), a large interferometer that is
undergoing construction in a high desert in Chile
Now that the reader has achieved some understanding of the
complex nature of the interstellar medium, he/she is ready to
read the article by Ewine van Dishoeck, Eric Herbst, and David
Neufeld on the abundance and chemistry of one molecule
dx.doi.org/10.1021/cr400579y | Chem. Rev. 2013, 113, 8707−8709
Chemical Reviews Editorial

waterin a variety of different sources. The authors discuss

three different chemical processes that lead to water formation:
low temperature ion-neutral chemistry, applicable to the gas
phase of cold dense cores; ice chemistry, applicable to the
chemistry that occurs on and in granular ice mantles; and high-
temperature gas-phase chemistry, which produces water
efficiently in regions over 300 K via neutral−neutral reactions.
Up to now, this Thematic Issue on Astrochemistry has by
and large bypassed planetary science, but we redeem ourselves
in the concluding article by Chris Bennett, Claire Pirim, and
Thomas Orlando, where chemical and physical processes that
cause weathering in solar system bodies are reviewed. The
processes are looked at both from the viewpoint of fundamental
physics and from that of actual observations and space
missions. John T. Yates, Jr. received his Ph.D. from MIT. He was an NRC
Postdoctoral Fellow at the National Bureau of Standards (now NIST)
We hope that you will enjoy the scientific riches in this
and then a staff member there for 17 years. During that time he was a
Thematic Issue and that you will come away with the
Sherman Fairchild Fellow at Caltech for one year. In 1982, he joined
knowledge that much interest in chemistry occurs outside the the Department of Chemistry at the University of Pittsburgh as R. K.
bounds of our home planet. Mellon Professor of Chemistry and as the founding Director of the
Eric Herbst Surface Science Center. He had a courtesy appointment in Physics at
Department of Chemistry, University of Virginia Pitt. In 2006 he moved to the University of Virginia Chemistry
John T. Yates, Jr. Department as Shannon Fellow and Professor of Chemistry. Among
Department of Chemistry, University of Virginia his honors are five ACS Awards and the Medard Welch Prize of the
American Vacuum Society. He is a Fellow of the American Physical
Society, the Institute of Physics, the American Chemical Society, and
AUTHOR INFORMATION
the American Vacuum Society. He recently became Associate Editor of
Notes Chemical Reviews. In 1996 he was elected to the National Academy of
Views expressed in this editorial are those of the authors and Sciences.
not necessarily the views of the ACS.
Biographies

Eric Herbst received his graduate education in physical chemistry at

Harvard University, under the direction of William Klemperer, where
he first began to study astrochemistry in addition to his major thesis
work in molecular-beam spectroscopy. After a post-doctoral stint at
Harvard, where he and Klemperer wrote a seminal paper on ion−
molecule chemistry in dense interstellar clouds, and a second
postdoctoral position at the University of Colorado under W. Carl
Lineberger, he held faculty positions at The College of William and
Mary in chemistry, at Duke University in physics, and at The Ohio
State University in physics and astronomy. He is currently
Commonwealth Professor of Chemistry at the University of Virginia,
with courtesy appointments in astronomy and physics. A scientific
editor of The Astrophysical Journal from 1998−2007, Herbst is a Fellow
of the American Physical Society and the Royal Society of Chemistry,
from which he received the Centenary Prize in 2004.

8709 dx.doi.org/10.1021/cr400579y | Chem. Rev. 2013, 113, 8707−8709