Molecules In Interstellar Space Research Articles

Single-Photon Ionization Induced New Covalent Bond Formation in Acrylonitrile(AN)-Pyrrole(Py) Clusters.

The formation of nitrogen-containing organic compounds is crucial for understanding chemical evolution and the origin of life in the interstellar medium (ISM). In this study, we explore whether acrylonitrile (AN) and pyrrole (Py) can form new nitrogen-containing compounds after single-photon ionization in their gaseous clusters by vacuum ultraviolet (VUV)-infrared (IR) spectroscopy and theoretical calculations. The results show that a strong linear H-bond is formed in neutral AN-Py, while cyclic or bicyclic H-bonded networks are formed in the neutral AN-Py2 cluster. It is found that the structure containing a new C-C covalent bond between two moieties in (AN-Py)+ is formed besides the formation of H-bonded structures after AN-Py is ionized by VUV light. In (AN-Py2)+ cluster cations, new C-C or C-N covalent bonds tend to be formed between two Py, with (Py)2+ as the core in the cluster. The results reveal that new covalent bonds are more likely to be formed between two Py species when AN and Py are present in the cationic clusters. These results provide spectroscopic evidence of the formation of new nitrogen-containing organic compounds from AN and Py induced by VUV, which are helpful for our understanding of the formation of diverse prebiotic molecules in interstellar space.

New potential energy surface and rotational deexcitation cross-sections of CNNC by para-H2 (jp = 0).

The objective of this study is to enhance our understanding of the existence of molecules in interstellar space by determining the collisional rate coefficients with the most prevalent species. The study examines the impact of para-H2 collisions, specifically when it is in its ground vibrational state with a nuclear spin of para-H2, i.e., jp = 0, on causing the rotational deexcitation of the diisocyanogen (CNNC) molecule. These scattering data are obtained as a result of spherically averaging a four-dimensional potential energy surface (4DPES) over the H2 orientations. Using the CCSD(T)-F12a approach and aug-cc-pVTZ basis sets, the ab initio 4DPES for the CNNC-H2 van der Waals system is calculated. The CNNC-para-H2 4DPES attains a global minimum of 221.38 cm-1 at the CNNC and H2 center of mass distance (R) of 3.1 Å. The method of close coupling calculations is employed for the purpose of calculating the cross-sectional data of CNNC with para-H2 (jp = 0), for total energies up to 1000 cm-1. Rate coefficients are computed over the temperature range of 1 K to 100 K. Propensity suggests that even Δj transitions are strongly preferred. The rate coefficients for CNNC-H2 are determined to be 0.90-2.95 times those of CNNC-He, which implies it is not reliable to estimate the H2 rate coefficients by multiplying the rate coefficients for CNNC-He collision with a scaling factor of 1.38.

Multiphoton breakdown of acetylene; formation of organic building block fragments.

Mass resolved REMPI spectra and electron and ion velocity map images were recorded for REMPI of acetylene in the case of two-photon resonant excitations to low lying 3p and 4p Rydberg states. Combined data analysis of ion signal intensities and electron and ion kinetic energy release distribution revealed multiphoton-fragmentation processes in terms of photodissociation and photoionization channels to form the molecular ion, C2H2+ and the fragment ions H+, C+, CH+, CH2+, C2+ and C2H+. The ratio of fragment ion formation over the parent ion formation increases with excitation energy. To a large extent, multiphoton-fragmentation involves the initial breakdown of the molecule into ground and excited state neutral fragments by two-, three- and four-photon dissociation processes prior to multiphoton ionization. The three-photon dissociation processes via superexcited molecular state(s) are found to be the most important and electronically excited fragment species playing a significant role in the overall multiphoton-fragmentation. Furthermore, the data are indicative of the involvement of secondary photodissociation processes and provide information on fragment energetics as well as state interactions. The question, whether acetylene could be an important source of building block fragments for the formation of organic molecules in interstellar space, is addressed.

Searching for biosignatures by their rotational spectrum: global fit and methyl group internal rotation features of dimethylsulphoxide up to 116 GHz

AbstractThe identification and quantification of molecules in interstellar space and atmospheres of planets in the solar systems and in exoplanets rely on spectroscopic methods and laboratory work is essential to provide the community with the spectral features needed to analyse cosmological observations. Rotational spectroscopy in particular, with its intrinsic high resolution, allows the unambiguous identification of biomolecular building blocks and biosignature gases which can be correlated with the origin of life or the identification of habitable planets. We report the extension of the measured rotational transition frequencies of dimethylsulphoxide and its 34S and 13C isotopologues in the millimetre wave range (59.6–78.4 GHz) by use of an absorption spectrometer based on the supersonic expansion technique. Hyperfine patterns related to the methyl group internal rotation were analysed in the microwave range region (6–18 GHz) with a Pulsed Jet Fourier Transform spectrometer at extremely high resolution (2 kHz) and reliable predictions up to 116 GHz are provided. The focus on sulphur-bearing molecules is motivated by the fact that sulphur is largely involved in the intra- and inter-molecular hydrogen bonds in proteins and although it is the 10th most abundant element in the known Universe, understanding its chemistry is still a matter of debate. Moreover, sulphur-bearing molecules, in particular dimethylsulphoxide, have been indicated as possible biosignature gases to be monitored in the search of habitable exoplanets.

The emergence of interstellar molecular complexity explained by interacting networks

Recent years have witnessed the detection of an increasing number of complex organic molecules in interstellar space, some of them being of prebiotic interest. Disentangling the origin of interstellar prebiotic chemistry and its connection to biochemistry and ultimately, to biology is an enormously challenging scientific goal where the application of complexity theory and network science has not been fully exploited. Encouraged by this idea, we present a theoretical and computational framework to model the evolution of simple networked structures toward complexity. In our environment, complex networks represent simplified chemical compounds and interact optimizing the dynamical importance of their nodes. We describe the emergence of a transition from simple networks toward complexity when the parameter representing the environment reaches a critical value. Notably, although our system does not attempt to model the rules of real chemistry nor is dependent on external input data, the results describe the emergence of complexity in the evolution of chemical diversity in the interstellar medium. Furthermore, they reveal an as yet unknown relationship between the abundances of molecules in dark clouds and the potential number of chemical reactions that yield them as products, supporting the ability of the conceptual framework presented here to shed light on real scenarios. Our work reinforces the notion that some of the properties that condition the extremely complex journey from the chemistry in space to prebiotic chemistry and finally, to life could show relatively simple and universal patterns.

Synthetic Approaches to Complex Organic Molecules in the Cold Interstellar Medium

The observation and synthesis of organic molecules in interstellar space is one of the most exciting and rapidly growing topics in astrochemistry. Spectroscopic observations especially with millimeter and submillimeter waves have resulted in the detection of more than 250 molecules in the interstellar clouds from which stars and planets are ultimately formed. In this review, we focus on the diverse suggestions made to explain the formation of Complex Organic Molecules (COMs) in the low-temperature interstellar medium. The dominant mechanisms at such low temperatures are still a matter of dispute, with both gas-phase and granular processes, occurring on and in ice mantles, thought to play a role. Granular mechanisms include both diffusive and nondiffusive processes. A granular explanation is strengthened by experiments at 10 K that indicate that the synthesis of large molecules on granular ice mantles under space-like conditions is exceedingly efficient, with and without external radiation. In addition, the bombardment of carbon-containing ice mantles in the laboratory by cosmic rays, which are mainly high-energy protons, can lead to organic species even at low temperatures. For processes on dust grains to be competitive at low temperatures, however, non-thermal desorption mechanisms must be invoked to explain why the organic molecules are detected in the gas phase. Although much remains to be learned, a better understanding of low-temperature organic syntheses in space will add both to our understanding of unusual chemical processes and the role of molecules in stellar evolution.

Cosmic Molecular Laboratories

Production and investigation of molecules in our laboratories on earth are regular, exciting and challenging tasks. Quite often big efforts are involved in these tasks. Therefore, before 1963, scientists were against the opinion for existence of molecules in interstellar space. After the discovery of radio-window in 1932, the first molecule OH was discovered in the interstellar space in 1963. Though the discovery was against the opinion of scientists, it created lot of interests in the cosmic molecules.

Chiral molecule found in space

Astronomers have discovered the first chiral molecule in interstellar space (Science 2016, DOI: 10.1126/science.aae0328). The discovery of propylene oxide in an interstellar cloud sets the stage for astronomers to explore chemical processes that led to the preference of one enantiomer over another in the formation of biomolecules on Earth. All organisms on Earth build their proteins almost entirely from left-handed enantiomers of amino acids. Scientists have long searched for the reason why life picked left-handed chirality over right-handed. The famous Murchison meteorite, which formed around the same time as our sun and landed in Australia in 1969, contains an abundance of amino acids, a slight excess of which are left-handed. This is significant because only a few percent excess of one enantiomer would be enough to push life in a direction of exclusive left or right handedness. Scientists want to know how far back this chiral preference extends in the

Molecular hydrogen interacts more strongly when rotationally excited at low temperatures leading to faster reactions.

The role of internal molecular degrees of freedom, such as rotation, has scarcely been explored experimentally in low-energy collisions despite their significance to cold and ultracold chemistry. Particularly important to astrochemistry is the case of the most abundant molecule in interstellar space, hydrogen, for which two spin isomers have been detected, one of which exists in its rotational ground state whereas the other is rotationally excited. Here we demonstrate that quantization of molecular rotation plays a key role in cold reaction dynamics, where rotationally excited ortho-hydrogen reacts faster due to a stronger long-range attraction. We observe rotational state-dependent non-Arrhenius universal scaling laws in chemi-ionization reactions of para-H2 and ortho-H2 by He(2(3)P2), spanning three orders of magnitude in temperature. Different scaling laws serve as a sensitive gauge that enables us to directly determine the exact nature of the long-range intermolecular interactions. Our results show that the quantum state of the molecular rotor determines whether or not anisotropic long-range interactions dominate cold collisions.

Charles Hard Townes: Remarkable Scientist and Inspiring Teacher

Charles Townes is renowned for his work elucidating the structure of molecules through microwave spectroscopy and for his invention of the maser and the laser. He also had a lifelong interest in astronomy, and in the later portion of his remarkable and long career devoted himself to astronomical research, pioneering the study of molecules in interstellar space and the development of infrared spectroscopy, first from the ground and then from airborne facilities. His interest in high angular resolution, as well as high spectral resolution observations, led to development of the first infrared spatial interferometer employing coherent signal processing techniques. In this short review I will only touch on some of Townes’ many scientific contributions, concentrating on astronomy, and will also give some personal thoughts about how he inspired students in their research, helping to make the “Townes Group” at the University of California, Berkeley, an ideal environment in which to start a career in research.

Vibration frequencies for searches of free triatomic molecules in interstellar space

More and more cold interstellar molecules are being discovered, the majority of them being organic. Perhaps it is time to consider the numerous small molecules that also await observation. We report progress in tabulating symmetric-stretch vibration frequencies for neutral main-group ground-state triatomic molecules, formed from period-2 atoms, which are not yet studied.

Using Computational Chemistry to Understand & Discover Chemical Reactions

Chemistry, the “science of matter,” is the investigation of the fabulously complex interchanges of atoms and bonds that happen constantly throughout our universe and within all living things. Computational chemistry is the computer modeling of chemistry using mathematical equations that come from physics. The field was made possible by advances in computer algorithms and computer power and continues to flourish in step with developments in those areas. Computational chemistry can be thought of as both a time-lapse video that slows down processes by a quadrillion-fold and an ultramicroscope that provides a billion-fold magnification. Computational chemists can quantitatively simulate simple chemistry, such as the chemical reactions between molecules in interstellar space. The chemistry inside a living organism is dramatically more complicated and cannot be simulated exactly, but even here computational chemistry enables understanding and leads to discovery of previously unrecognized phenomena. This essay describes how computational chemistry has evolved into a potent force for progress in chemistry in the twenty-first century.

Detection of a branched alkyl molecule in the interstellar medium: iso-propyl cyanide.

The largest noncyclic molecules detected in the interstellar medium (ISM) are organic with a straight-chain carbon backbone. We report an interstellar detection of a branched alkyl molecule, iso-propyl cyanide (i-C3H7CN), with an abundance 0.4 times that of its straight-chain structural isomer. This detection suggests that branched carbon-chain molecules may be generally abundant in the ISM. Our astrochemical model indicates that both isomers are produced within or upon dust grain ice mantles through the addition of molecular radicals, albeit via differing reaction pathways. The production of iso-propyl cyanide appears to require the addition of a functional group to a nonterminal carbon in the chain. Its detection therefore bodes well for the presence in the ISM of amino acids, for which such side-chain structure is a key characteristic.

Carbon chains branch out on space dust

Interstellar Chemistry Meteorites found on Earth contain a wide range of complex constituent molecules, including amino acids. Astrochemists proposed the existence of these molecules in interstellar space in the 1980s, but detections have been elusive. Belloche et al. used the ALMA telescope array in Chile to observe the massive star-forming region Sgr B2. There, the vast quantities of gas enabled detection of even sparsely distributed species such as iso -propyl cyanide. Despite being difficult to detect, such nonlinear organic molecules may be common. The formation of branched molecules is important, given the analogous structure of familiar amino acids — some of the building blocks for life. Science , this issue p. [1584][1] [1]: /lookup/doi/10.1126/science.1256678

Extending the Limits of Rotationally Resolved Absorption Spectroscopy: Pyrene

We report the rotationally resolved gas phase spectrum of pyrene (C16H10), which is now the largest molecule to be observed with rotational resolution using absorption spectroscopy. This represents a significant advance in the application of absorption spectroscopy to large carbon-containing molecules of fundamental chemical and astronomical importance. Such spectra will facilitate the search for large and highly symmetric molecules in interstellar space, where they may be abundant but cannot be detected without the support of high-resolution laboratory spectra. Detailed assignment and analysis of our spectrum indicates that pyrene is the most rigid rotor yet observed, and that a supersonic expansion cools both the rotational and vibrational temperatures of pyrene vapor produced in an oven source.

Optical spectrum of proflavine and its ions

Motivated by possible astrophysical and biological applications we calculate visible and near UV spectral lines of proflavine (C 13H 11N 3, 3,6-diaminoacridine) in vacuum, as well as its anion, cation, and dication. The pseudopotential density functional and time-dependent density functional methods are used. We find a good agreement in spectral line positions calculated by two real-time propagation methods and the Lanczos chain method. Spectra of proflavine and its ions show characteristic UV lines which are good candidates for a detection of these molecules in interstellar space and various biological processes.

FIRST MOLECULAR ANION IDENTIFIED IN SPACE

ONCE THOUGHT TOO FRAGILE to exist in the severe environment of outer space, molecular anions may actually be ubiquitous there. For the first time, researchers have observed in astronomical clouds large amounts of a negatively charged molecule: the hexatriyne anion, or C 6 H - ( Astrophys. J. 2006 , 652, L141). Detection of the molecule in interstellar space overturns the belief that radiation would quickly strip an anion of its extra electron, yielding a radical. The finding, reported by Michael C. McCarthy, Patrick Thaddeus, and colleagues at the Harvard-Smithsonian Center for Astrophysics, in Cambridge, Mass., also solves a spectral puzzle, identifying C 6 H - as the source of a mysterious set of rotational lines discovered in a molecular cloud over 10 years ago. Observers say the addition of anions to the mix of known molecules in space will alter the field of interstellar chemistry. I would say this is the most important observation since the first detection of positive ions in ...

Relaxation paths for single modes of vibrations in isolated molecules

A numerical simulation of vibrational excitation of molecules was devised and used to excite computational models of common molecules into a prescribed, pure, normal vibration mode in the ground electronic state, with varying, controllable energy content. The redistribution of this energy (either non-chaotic or irreversible IVR) within the isolated, free molecule is then followed in time with a view to determining the coupling strength between modes. This work was triggered by the need to predict the general characters of the infrared spectra to be expected from molecules in interstellar space, after being excited by photon absorption or reaction with a radical. It is found that IVR from a pure normal mode is very ‘restricted’ indeed at energy contents of one mode quantum or so. However, as this is increased, or when the excitation is localized, our approach allows us to isolate, describe and quantify a number of interesting phenomena, known to chemists and in nonlinear mechanics, but difficult to demonstrate experimentally: frequency dragging, mode locking or quenching or, still, instability near a potential surface crossing, the first step to generalized chaos as the energy content per mode is increased.

Cyanomethylidyne: A Reactive Carbyne Radical

The cyanomethylidyne radical (CCN) has been a long-standing subject of extensive structural and spectroscopic studies. However, its chemical reactivity has received rather little attention. Recently, we studied the reaction of CCN with the simplest alkane, CH4, which follows a mechanism of carbyne insertion-dissociation rather than that of direct H abstraction proposed by a recent experimental study. However, we are aware that alkanes like CH4 bear no electron lone pairs and thus are not ideal diagnostic molecules for distinguishing between the carbyne-insertion and H-abstraction mechanisms. Hence, we chose a series of sigma-bonded molecules HX (X=OH, NH2, and F) which bear electron lone pairs and are better diagnostics for carbyne-insertion behavior. The new results at the CCSD(T)/6-311+G(2df,p)//B3LYP/6-311G(d,p)+ZPVE, CCSD(T)/aug-cc-pVTZ//B3LYP/6-311G(d,p)+ZPVE, G2M(CC1), and MC-QCISD//B3LYP/6-31G(d)+ZPVE levels definitively confirm the carbyne-insertion behavior of the CCN radical towards HX. In addition, we make the first attempt to understand the reactivity of the CCN radical toward pi-bonded molecules, using the CCN+C2H2 model reaction. This reaction involves carbenoid addition to the C[triple chemical bond]C bond without a potential-energy barrier to form a C3 three-membered cyclic intermediate followed by H extrusion. Therefore, the reactions of CCN with both sigma- and pi-bonded molecules conclusively show that CCN is a reactive carbyne radical and may be more reactive than the well-known CN radical. Future experimental studies, especially on product characterization, are strongly desired to test our proposed carbyne mechanism. The studied reactions of CCN with CH4, NH3, H2O, and C2H2 could be of interest to combustion science and astrophysics, and they could provide efficient routes to form novel cyano-containing molecules in interstellar space.

The formation of interstellar molecules via reactions on dust grain surfaces

The formation of molecules in interstellar space via reactions on the surface of dust grains has been the subject of numerous theoretical studies, since a very important reaction, the formation of molecular hydrogen, is thought to occur primarily on dust. Beginning with the very first experiments of the formation of H2 on a dust grain analogue by Pirronello et al., in 1997, and continuing today, it has been possible to study and characterize the processes of molecular hydrogen formation on realistic analogues of dust grains with increasing sophistication. In our laboratory, we use state-of-the-art surface science techniques to come as closely as technically possible to the conditions of molecule formation in the ISM. Here, we present the results of studies on the mechanisms and rate of formation of molecular hydrogen on dust grain analogues.