Large polycyclic aromatic hydrocarbon (PAH) molecules carry the infrared (IR) emission features that dominate the spectra of most galactic and extragalactic sources. This review surveys the observed mid-IR characteristics of these emission features and summarizes laboratory and theoretical studies of the spectral characteristics of PAHs and the derived intrinsic properties of emitting interstellar PAHs. Dedicated experimental studies have provided critical input for detailed astronomical models that probe the origin and evolution of interstellar PAHs and their role in the universe. The physics and chemistry of PAHs are discussed, emphasizing the contribution of these species to the photoelectric heating and the ionization balance of the interstellar gas and to the formation of small hydrocarbon radicals and carbon chains. Together, these studies demonstrate that PAHs are abundant, ubiquitous, and a dominant force in the interstellar medium of galaxies.

Interstellar Polycyclic Aromatic Hydrocarbon Molecules

Graphene has a unique atom-thick two-dimensional (2D) structure, high conductivity and charge mobility, huge specific surface area, excellent mechanical, thermal and electrical properties. Thus, it has been regarded as an important component for functional materials, especially for developing a variety of catalysts. In this review, we summarize the recent advancements in synthesizing graphene based new catalysts, and their applications in organic synthesis, sensors, environmental protection and energy related systems.

Graphene based catalysts

1.1. Historical Background Hydrogen bonds1,2 are one of the principal intermolecular forces. A special class are ionic hydrogen bonds (IHBs) that form between ions and molecules with bonds strengths of 5-35 kcal/mol, up to a third of the strength of covalent bonds. These strong interactions are critical, for example, in ionic clusters and nucleation, in electrolytes, ion solvation, and acid-base chemistry, in the structures of ionic crystals, surfaces, silicates, and clays, in surface adsorption, and in self-assembly in supramolecular chemistry and molecular crystals.3 IHBs are also important in bioenergetics including protein folding, enzyme active centers, formation of membranes and proton transport, and biomolecular recognition. With such wide-ranging roles, the fundamental properties of IHB interactions need to be understood. The energetics of IHB interactions cannot be isolated and quantified in the condensed phase. However, these interactions can be isolated and studied quantitatively in gas phase. These studies lead to a fundamental understanding of relations between IHB bond strengths and molecular structure, the solvation of ions, especially in the critical inner shells, and acid-based phenomena and bioenergetics. This review will present the basic insights that have been obtained in the past four decades. It will present a comprehensive review of the thermochemistry and its structural implications obtained from ab initio calculations. Relevant recent results from spectroscopy will be also illustrated. The advent of variable temperature high-pressure mass spectrometry (HPMS) introduced by Field and co-workers in the 1960s4 and pulsed high-pressure mass spectrometry (PHPMS) introduced by Kebarle in the late 1960s5 have been particularly significant. These workers realized that at pressures of several torrs and gas densities of 1016-1017 cm-3 in ion sources, ions can undergo 103-106 collisions with neutral molecules during typical residence times of 0.1-10 ms and establish thermal ion populations and * E-mail: m.mautner@solis1.com. 213 Chem. Rev. 2005, 105, 213−284

http://www.astro-ecology.com/PDFTheIonicHydrogenBondChemicalReviews2005Paper.pdf

The Ionic Hydrogen Bond

Gas-phase infrared multiple photon dissociation spectroscopy of mass-selected molecular ions

▪ Abstract This review provides a historical context for our understanding of the hydration shell surrounding halide ions and illustrates how the cluster systems can be used, in combination with theory, to elucidate the behavior of water molecules in direct contact with the anion. We discuss how vibrational predissociation spectroscopy, carried out with weakly bound argon atoms, has been employed to deduce the morphology of the small water networks attached to anions in the primary steps of hydration. We emphasize the importance of charge-transfer in the binary interaction, and discuss how this process affects the structures of the larger networks. Finally, we survey how the negatively charged water clusters (H2O)n− are providing a molecular-level perspective on how diffuse excess electrons interact with the water networks.

Molecular aspects of halide ion hydration: the cluster approach.

Protonated Benzene: IR Spectrum and Structure of C6H7+ †

Protonation of aromatic molecules: competition between ring and oxygen protonation of phenol (Ph) revealed by IR spectra of PhH+–Arn

Infrared spectra of the phenol–Ar and phenol–N2 cations: proton-bound versus π-bound structures

Keywords: arenes ; aromatic substitution ; carbocations ; IR spectroscopy ; polycycles Reference EPFL-ARTICLE-225598doi:10.1002/anie.200701838 Record created on 2017-02-13, modified on 2017-05-12

Nicola Solcà

Papers

Protonated Benzene: IR Spectrum and Structure of C6H7+ †

Protonation of aromatic molecules: competition between ring and oxygen protonation of phenol (Ph) revealed by IR spectra of PhH+–Arn

Infrared spectra of the phenol–Ar and phenol–N2 cations: proton-bound versus π-bound structures

Infrared spectra of isolated protonated polycyclic aromatic hydrocarbons: protonated naphthalene.

IR spectrum of the benzene–water cation: direct evidence for a hydrogen-bonded charge–dipole complex