Lester Andrews

Bio: Lester Andrews is an academic researcher from University of Virginia. The author has contributed to research in topics: Infrared spectroscopy & Molecule. The author has an hindex of 68, co-authored 888 publications receiving 24613 citations. Previous affiliations of Lester Andrews include Ames Research Center & Environmental Molecular Sciences Laboratory.

Laser-evaporated aluminum atom reactions with halogen molecules. Infrared spectra of AlXn (X = F, Cl, Br, I; n = 1-3) in solid argon

Abstract: Reactions of laser-evaporated aluminum atoms with molecular fluorine, chlorine, bromine, and iodine in excess argon during condensation onto a CsI window at 11 ± 1 K produced the AlXn (X = F, Cl, Br, I and n = 1−3) and Al2X6 molecules, which were characterized by infrared absorption spectroscopy. Low laser power favored the primary reaction product AlX and AlX2 transient species over the more stable secondary reaction product AlX3 molecules. Chlorine and bromine isotopic structures substantiated the molecular identifications and vibrational assignments. DFT calculations were done for the AlCln and AlBrn series to support the vibrational assignments. Possible Al2Cl4 structures were also explored by DFT calculations, and evidence is presented for a distorted Cl2AlCl2Al structure. The present study provides further evidence for transient aluminum dihalide radicals for the four halogens.

Hydrogen elimination from ethylene by laser-ablated Zr atoms: An infrared spectroscopic investigation of the reaction intermediates in a solid argon matrix

Abstract: Intermediates of the hydrogen elimination reaction of ethylene by laser-ablated Zr atoms have been isolated in an argon matrix and investigated by means of infrared spectroscopy. The strong absorptions in the region of 1500−1660 cm-1 are due to the Zr−H stretching modes of several intermediates. There are at least three different groups of product absorptions based on the behaviors upon broad-band photolysis and annealing. Among them, the insertion and dihydrido complexes, presumed in previous studies of the hydrogen elimination of ethylene by Zr atoms, are identified. In addition, the remaining Zr−H stretching absorptions, along with absorptions in the C⋮C stretching and other regions, suggest that ethynyl zirconium trihydride is also formed in the hydrogen elimination reaction. Formation of this compound is consistent with the fact that C2H2 and C2D2 as well as CHCD are produced in the reaction of Zr + CH2CD2. Density functional theory calculations for the reaction intermediates are also carried out, an...

Infrared spectra of antimony and bismuth hydrides in solid matrixes

Abstract: Laser-ablated Sb and Bi atoms react with hydrogen during condensation in excess hydrogen, neon, and argon to form the SbH and BiH diatomic molecules. In addition the new Group 15 MH2 dihydride radicals and the MH3 trihydrides are observed for Sb and Bi metals. Although BiH3 is of limited stability in the gas phase, BiH3 is formed by further H atom reactions with BiH2 in solid hydrogen and neon. No evidence is found for the thermochemically unstable BiH5 molecule.

Infrared and DFT Investigations of the XC⋮ReX3 and HC⋮ReX3 Complexes: Jahn−Teller Distortion and the Methylidyne C−X(H) Stretching Absorptions

Abstract: The XC[triple bond]ReX3 complexes (X = F, Cl) are produced by CX(4) reaction with laser-ablated Re atoms, following oxidative C-X insertion and alpha-halogen migration in favor of the carbon-metal triple bond and are identified through the observation of characteristic absorptions in the argon matrix infrared spectra and comparison with vibrational frequencies calculated by density functional theory. The methylidyne C-F and C-Cl stretching absorptions are observed near 1584 and 1328 cm-1, and the C-H stretching modes for HC[triple bond]ReX3 at 3104 and 3097 cm(-1), respectively, which are substantially higher than the precursor stretching modes and in agreement with the general trend that higher s-orbital character in carbon hybridization leads to a higher stretching frequency. The Jahn-Teller effect in the doublet-state XC[triple bond]ReX3 and HC[triple bond]ReX3 complexes gives rise to distorted structures with Cs symmetry and two equivalent longer Re-X bonds and one slightly shorter Re-X bond.

A Chemist's Guide to Density Functional Theory

Abstract: "Chemists familiar with conventional quantum mechanics will applaud and benefit greatly from this particularly instructive, thorough and clearly written exposition of density functional theory: its basis, concepts, terms, implementation, and performance in diverse applications. Users of DFT for structure, energy, and molecular property computations, as well as reaction mechanism studies, are guided to the optimum choices of the most effective methods. Well done!" Paul von RaguE Schleyer "A conspicuous hole in the computational chemist's library is nicely filled by this book, which provides a wide-ranging and pragmatic view of the subject.[...It] should justifiably become the favorite text on the subject for practioneers who aim to use DFT to solve chemical problems." J. F. Stanton, J. Am. Chem. Soc. "The authors' aim is to guide the chemist through basic theoretical and related technical aspects of DFT at an easy-to-understand theoretical level. They succeed admirably." P. C. H. Mitchell, Appl. Organomet. Chem. "The authors have done an excellent service to the chemical community. [...] A Chemist's Guide to Density Functional Theory is exactly what the title suggests. It should be an invaluable source of insight and knowledge for many chemists using DFT approaches to solve chemical problems." M. Kaupp, Angew. Chem.

The density functional formalism, its applications and prospects

Abstract: A scheme that reduces the calculations of ground-state properties of systems of interacting particles exactly to the solution of single-particle Hartree-type equations has obvious advantages. It is not surprising, then, that the density functional formalism, which provides a way of doing this, has received much attention in the past two decades. The quality of the energy surfaces calculated using a simple local-density approximation for exchange and correlation exceeds by far the original expectations. In this work, the authors survey the formalism and some of its applications (in particular to atoms and small molecules) and discuss the reasons for the successes and failures of the local-density approximation and some of its modifications.

The Halogen Bond

Abstract: The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

Generation and Detection of Reactive Oxygen Species in Photocatalysis

Abstract: The detection methods and generation mechanisms of the intrinsic reactive oxygen species (ROS), i.e., superoxide anion radical (•O2–), hydrogen peroxide (H2O2), singlet oxygen (1O2), and hydroxyl radical (•OH) in photocatalysis, were surveyed comprehensively. Consequently, the major photocatalyst used in heterogeneous photocatalytic systems was found to be TiO2. However, besides TiO2 some representative photocatalysts were also involved in the discussion. Among the various issues we focused on the detection methods and generation reactions of ROS in the aqueous suspensions of photocatalysts. On the careful account of the experimental results presented so far, we proposed the following apprehension: adsorbed •OH could be regarded as trapped holes, which are involved in a rapid adsorption–desorption equilibrium at the TiO2–solution interface. Because the equilibrium shifts to the adsorption side, trapped holes must be actually the dominant oxidation species whereas •OH in solution would exert the reactivity...

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Abstract: : The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg