Matthew L. Costen

Bio: Matthew L. Costen is an academic researcher from Heriot-Watt University. The author has contributed to research in topics: Scattering & Inelastic scattering. The author has an hindex of 26, co-authored 72 publications receiving 1556 citations. Previous affiliations of Matthew L. Costen include University of Oxford & University of Edinburgh.

Nanosegregation and Structuring in the Bulk and at the Surface of Ionic-Liquid Mixtures

Abstract: Ionic-liquid (IL) mixtures hold great promise, as they allow liquids with a wide range of properties to be formed by mixing two common components rather than by synthesizing a large array of pure ILs with different chemical structures. In addition, these mixtures can exhibit a range of properties and structural organization that depend on their composition, which opens up new possibilities for the composition-dependent control of IL properties for particular applications. However, the fundamental properties, structure, and dynamics of IL mixtures are currently poorly understood, which limits their more widespread application. This article presents the first comprehensive investigation into the bulk and surface properties of IL mixtures formed from two commonly encountered ILs: 1-ethyl-3-methylimidazolium and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N] and [C12mim][Tf2N]). Physical property measurements (viscosity, conductivity, and density) reveal that these IL mixtures ...

Dynamics of Inelastic Scattering of OH Radicals from Reactive and Inert Liquid Surfaces

Abstract: The inelastic scattering of gas-phase OH radicals from a liquid hydrocarbon and a liquid perfluorinated polyether (PFPE) has been investigated. The surfaces examined were the potentially reactive, branched hydrocarbon squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) and the inert PFPE Krytox 1506 (F−[CF(CF3)CF2O]14ave−CF2CF3). Superthermal OH was formed by 355-nm laser photolysis of a low pressure of HONO above the liquid surface. Laser-induced fluorescence (LIF) was used to determine the relative yields and nascent translational and rotational distributions of OH (v′ = 0). The time-of-flight profiles from both liquids can be resolved, at least empirically, into two components. The dominant, faster component is consistent with direct, inelastic scattering. It has a higher average translational energy from PFPE than from squalane. This faster OH also has a higher Boltzmann-like rotational temperature for PFPE (655 ± 45 K) than for squalane (473 ± 27 K), in both cases considerably hotter than the in...

Vector signatures of adiabatic and diabatic dynamics in the photodissociation of ICN

Abstract: Nascent Doppler profiles of CN (X 2∑+) fragments from the A band photodissociation of room temperature ICN have been measured using high-resolution transient frequency modulated absorption spectroscopy. Results for dissociation at 222 nm, 248 nm, 266 nm, and 308 nm are presented. From the Doppler profiles of multiple CN states, we determine branching ratios of the coincident atomic iodine states, and bipolar moments characterizing the CN velocity and angular momentum anisotropy. The measurements provide sensitive tests of the strengths of optical coupling to the excited states contributing to the A band continuum, and the adiabatic and diabatic dynamics leading to the observed product states. Precise velocity measurements resolve differences in the average energy of the ICN molecules leading to selected fragment channels. We find a bond energy for ICN of 26 980±100 cm−1, somewhat higher than previous literature values.

Do vectors point the way to understanding energy transfer in molecular collisions

Abstract: This tutorial review examines the proposition that vector properties reveal more about the underlying potential energy surfaces controlling the inelastic exchange of energy in intermolecular collisions than conventional scalar measurements. Exciting recent experimental progress is summarized in the form of six selected cases studies. The new information that has been extracted is compared with the predictions of complementary theory. Likely future prospects and promising avenues for further progress are discussed. The treatment should appeal to all those with interests in the forces governing intermolecular interactions, especially in gas-phase collisions.

Orientation and alignment depolarization in OH(X Π2)+Ar/He collisions

Abstract: The depolarization of OH(X Π23/2,v=0,J=1.5–6.5,e) rotational angular momentum (RAM) in collisions with He and Ar under thermal conditions (298 K) has been studied using two-color polarization spectroscopy (PS). Orientation or alignment of the OH RAM was achieved using circularly or linearly polarized pulsed excitation, respectively, on the off-diagonal OH A Σ2+−X Π2(1,0) band. The evolution of the ground-state OH(X) RAM polarization, exclusively, was probed using an independent, linearly polarized pulse tuned to the diagonal OH A Σ2+−X Π2(0,0) band. The PS signal decay rate constant kPS decreases with increasing rotational quantum number for OH(X)+Ar but does not vary monotonically for OH(X)+He. The measured kPS equals the sum kRET+kΛ+kdep, where kRET, kΛ, and kdep are the rate constants for rotational energy transfer, Λ-doublet changing collisions, and rotationally elastic depolarization (of orientation or alignment of the OH(X) angular momentum, as specified), respectively. Values of kdep can be extract...

Plasma-liquid interactions: A review and roadmap

Abstract: Plasma–liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on non-equilibrium plasmas.

A new criterion for the determination of molecular structures from ground state rotational constants

Abstract: Kraitchman has shown that a single isotopic substitution on an atom is sufficient to determine directly the coordinates of that atom with respect to the principal axes of the original molecule. Kraitchman's formulas represent exact solutions of the equations for the equilibrium moments of inertia. However, the effects of the zero‐point vibrations are such that the coordinates obtained by substitution from the ground state moments of inertia I0 are systematically less than r0. These coordinates have here been called r (substitution) or rs, and it is found that rs≃(r0+re)/2, and Is= ∑ imirsi2≃(I0+Ie)/2.In the usual method of solution, the coordinate of one atom is determined from the equation for I0, and therefore the difference I0—Is must be made up by this one coordinate. This introduces a large error in the structures normally determined from ground state constants, and results in variations of 0.01 A in structures determined from different sets of isotopic species. If instead, we obtain the structure on...

Multiphase chemistry at the atmosphere-biosphere interface influencing climate and public health in the anthropocene.

Abstract: This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Review pubs.acs.org/CR Multiphase Chemistry at the Atmosphere−Biosphere Interface Influencing Climate and Public Health in the Anthropocene Ulrich Po schl* and Manabu Shiraiwa* Multiphase Chemistry Department, Max Planck Institute for Chemistry, 55128 Mainz, Germany air contaminants (SHCC) and their multiphase chemical interactions at the atmosphere−biosphere interface, including human lungs and skin, plant leaves, cryptogamic covers, soil, and aquatic surfaces. After an overview of different groups of SHCC, we address the chemical interactions of reactive oxygen species and reactive nitrogen species (ROS, RNS), primary biological and secondary organic aerosols (PBA, SOA), as well as carbonaceous combustion aerosols (CCA) including soot, black/elemental carbon, polycyclic aromatic hydrocarbons, and related compounds (PAH, PAC). ROS and RNS interact strongly with other SHCC and are central to both atmospheric and physiological processes and their coupling through the atmosphere−biosphere interface, for example, in the formation and aging of biogenic and combustion aerosols as well as in CONTENTS inflammatory and allergic immune responses triggered by air pollution. Deposition of atmospheric ROS/RNS and aerosols 1. Introduction and Motivation can damage biological tissues, modify surface microbiomes, and 2. Health- and Climate-Relevant Air Contaminants induce oxidative stress through Fenton-like reactions and 2.1. Reactive Oxygen and Nitrogen Species immune responses. The chemical mechanisms and kinetics are 2.2. Primary Biological Aerosols not yet fully elucidated, but the available evidence suggests that 2.3. Secondary Organic Aerosols multiphase processes are crucial for the assessment, prediction, 2.4. Carbonaceous Combustion Aerosols and handling of air quality, climate, and public health. Caution 2.5. Other Air Contaminants Linking Atmospher- should be taken to avoid that human activities shaping the ic and Physiological Chemistry Anthropocene create a hazardous or pathogenic atmosphere 3. Multiphase Chemical Reactions at Specific Bio- overloaded with allergenic, corrosive, toxic, or infectious logical Interfaces contaminants. 3.1. Lung Lining Fluid Multiphase chemistry deals with chemical reactions, trans- 3.2. Human Skin port processes, and transformations between gaseous, liquid, 3.3. Plant Surfaces and Cryptogamic Covers and solid matter. These processes are essential for Earth system 3.4. Soil and Aquatic Surfaces science and climate research as well as for life and health 4. Conclusions and Outlook sciences on molecular and global levels, bridging a wide range Author Information of spatial and temporal scales from below nanometers to Corresponding Authors thousands of kilometers and from less than nanoseconds to Notes years and millennia as illustrated in Figure 1. Biographies From a chemical perspective, life and the metabolism of most Acknowledgments living organisms can be regarded as multiphase processes References involving gases like oxygen and carbon dioxide; liquids like water, blood, lymph, and plant sap; and solid or semisolid substances like bone, tissue, skin, wood, and cellular 1. INTRODUCTION AND MOTIVATION membranes. Even primitive forms of life and metabolic activity Multiphase chemistry plays a vital role in the Earth system, under anaerobic conditions generally involve multiple liquid climate, and health. Chemical reactions, mass transport, and and solid or semisolid phases structured by cells, organelles, and phase transitions between gases, liquids, and solids are essential membranes. 2 On global scales, the biogeochemical cycling of for the interaction and coevolution of life and climate. chemical compounds and elements, which can be regarded as Knowledge of the mechanisms and kinetics of these processes the metabolism of planet Earth, also involves chemical is also required to address societally relevant questions of global reactions, mass transport, and phase transitions within and environmental change and public health in the Anthropocene, that is, in the present era of globally pervasive and steeply Special Issue: 2015 Chemistry in Climate increasing human influence on planet Earth. 1 In this work, we review the current scientific understanding and recent advances Received: September 1, 2014 in the investigation of short-lived health- and climate-relevant Published: April 9, 2015 © 2015 American Chemical Society DOI: 10.1021/cr500487s Chem. Rev. 2015, 115, 4440−4475

Rotational Spectroscopy of Diatomic Molecules

Abstract: 1. General introduction 2. The separation of nuclear and electronic motion 3. The electronic hamiltonian 4. Interactions arising from nuclear magnetic and electric moments 5. Angular momentum theory and spherical tensor algebra 6. Electronic and vibrational states 7. Derivation of the effective hamiltonian 8. Molecular beam magnetic and electric resonance 9. Microwave and far-infrared magnetic resonance 10. Pure rotational spectroscopy 11. Double resonance spectroscopy Appendices.

Infrared spectroscopy of helium nanodroplets: novel methods for physics and chemistry

Abstract: Helium nanodroplets have emerged as a new and exciting medium for studying the structure and dynamics of both this quantum solvent and impurities that can be doped into (onto) and grown inside (on the surface) of the droplets. Spectroscopic studies of these molecular impurities can provide detailed information on helium as a solvent and its interaction with the solute. This is particularly important given that helium is completely transparent to photons below 20 eV, making the direct spectroscopic study of liquid helium problematic. Since liquid helium is an extremely weak solvent, the corresponding perturbations to the spectrum of the solute molecules are often minor; really only evident because of the high resolution that is often achieved in such studies. As a result, helium nanodroplet spectra often resemble the corresponding gas-phase results. Indeed, for the case of rotational spectroscopy, the gas-phase Hamiltonian is often sufficient to describe the system, with the effects of the solvent being to...