Interstellar Formation of Nitrogen Heteroaromatics [Indole, CHN; Pyrrole, CHN; Aniline, CHNH]: Key Precursors to Amino Acids and Nucleobases.

Nitrogen-substituted polycyclic aromatic hydrocarbons (NPAHs) are not only fundamental building blocks in the prebiotic synthesis of vital biomolecules such as amino acids and nucleobases of DNA and RNA but also a potential source of the prominent unidentified 6.2 μm interstellar absorption band. Although NPAHs have been detected in meteorites and are believed to be ubiquitous in the universe, their formation mechanisms in deep space have remained largely elusive.

Identification of a prismatic PN molecule formed from electron irradiated phosphine-nitrogen ices.

Polyhedral nitrogen containing molecules such as prismatic PN - a hitherto elusive isovalent species of prismane (CH) - have attracted particular attention from the theoretical, physical, and synthetic chemistry communities. Here we report on the preparation of prismatic PN [1,2,3-triaza-4,5,6-triphosphatetracyclo[2.2.

On the Analysis of High Harmonic Generation Spectra of Atoms and Molecules Using Molecular Electrostatic Potential.

One of the factors that limits the application of the single active electron (SAE) formalism to simulate the high harmonic generation (HHG) spectra of atoms and molecules using the time-dependent Schrödinger equation (TDSE) is the unknown model effective one-dimensional potential energy (()) curve for the SAE. In the present contribution, we show that () can be constructed from the one-dimensional molecular electrostatic potential (MEP) of the respective cation to access theoretical HHG spectra not only for simple atoms but also for multielectron complex molecules.

A Photoionization Reflectron Time-of-Flight Mass Spectrometric Study on the Detection of Ethynamine (HCCNH ) and 2H-Azirine (c-H CCHN).

Ices of acetylene (C H ) and ammonia (NH ) were irradiated with energetic electrons to simulate interstellar ices processed by galactic cosmic rays in order to investigate the formation of C H N isomers. Supported by quantum chemical calculations, experiments detected product molecules as they sublime from the ices using photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS). Isotopically-labeled ices confirmed the C H N assignments while photon energies of 8.

A Photoionization Study on the Detection of 1-Sila Glycolaldehyde (HSiOCH OH), 2-Sila Acetic Acid (H SiCOOH), and 1,2-Disila Acetaldehyde (HSiOSiH ).

The identification of silicon-substituted, complex organics carrying multiple functional groups by classical infrared spectroscopy is challenging because the group frequencies of functional groups often overlap. Photoionization (PI) reflectron time-of-fight mass spectrometry (ReTOF-MS) in combination with temperature-programmed desorption (TPD) holds certain advantages because molecules are identified after sublimation from the matrix into in the gas phase based on distinct ionization energies and sublimation temperatures. In this study, we reveal the detection of 1-silaglycolaldehyde (HSiOCH OH), 2-sila-acetic acid (H SiCOOH), and 1,2-disila-acetaldehyde (H SiSiHO)-the silicon analogues of the well-known glycolaldehyde (HCOCH OH), acetic acid (H CCOOH), and acetaldehyde (H CCHO), in the gas phase after preparation in silane (SiH )-carbon dioxide ices exposed to energetic electrons and subliming the neutral reaction products formed within the ices into the gas phase.

Experimental Evidence of Sensitivity of the High Harmonic Generation to Hydrogen Bonding.

The influence of hydrogen bonding and the associated attosecond hole delocalization on the high-order harmonic generation (HHG) process is investigated with the help of hydrogen-bonded binary mixture of acetonitrile and chloroform solvent vapors. We observe a strong enhancement of the HH yield compared to the results obtained with pure samples. We propose that the observed increase of HHG efficiency is due to the presence of hydrogen-bonded binary mixture.

Molecular attochemistry in non-polar liquid environments: ultrafast charge migration dynamics through gold-thiolate and gold-selenolate linkages.

Molecular attosecond science has already started contributing to our fundamental understanding of ultrafast purely electron dynamics in isolated molecules under vacuum. Extending attosecond science to the liquid phase is expected to offer new insight into the influence of a surrounding solvent environment on the attosecond electron dynamics in solvated molecules. A systematic theoretical investigation of the attochemistry of solvated molecules would help one design attosecond experiments under ambient conditions to explore the attochemistry in a liquid environment.

Attochemistry of Ionized Halogen, Chalcogen, Pnicogen, and Tetrel Noncovalent Bonded Clusters.

In general, charge migration can occur via pure electron-electron correlation and relaxation or via coupling with nuclear motion. We must understand both aspects of charge migration through the non-hydrogen noncovalent bonds to harness full potential of the halogen-, chalcogen-, pnicogen- and tetrel-bonded photosensitive functional materials. This feature article, however, is focused on the pure relaxation- and correlation-driven charge migration, subsequent charge localization, and finally on charge-directed reactivity in the non-hydrogen noncovalent bonded clusters.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization.

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes.