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.

Infrared spectroscopic and theoretical studies of the OTiF2, OZrF2 and OHfF2 molecules with terminal oxo ligands.

Abstract: The isolated group 4 metal oxydifluoride molecules OMF2 (M = Ti, Zr, Hf) with terminal oxo groups are produced specifically on the spontaneous reactions of metal atoms with OF2 through annealing in solid argon. The product structures and vibrational spectra are characterized using matrix isolation infrared spectroscopy as well as B3LYP density functional and CCSD(T) frequency calculations. OTiF2 is predicted to have a planar structure while both OZrF2 and OHfF2 possess pyramidal structures, all with singlet ground states. Three infrared absorptions are observed for each product molecule, one M–O and two M–F stretching modes, and assignments of these molecules are further supported by the corresponding 18O shifts. The molecular orbitals of the group 4 OMF2 molecules show triple bond character for the terminal oxo groups, which are also supported by an NBO analysis. These molecular orbitals include a σ bond (O2p + Tisd hybrid), a normal electron pair π bond (O2p + Tid), and a dative π bond arising from O lone pair donation to the overlapping Ti d orbital. The M–O bond dissociation energies for OMF2 are comparable to those in the diatomic oxide molecules. The OTiF intermediate is also observed through two slightly lower frequency bond stretching modes, and its yield is increased in complementary TiO + F2 experiments. Finally, the formation of group 4 OMF2 molecules is highly exothermic due to the weak O–F bonds in OF2 as well as the strong new MO and M–F bonds formed.

Infrared spectra of the CH3-MX and CH2-MHX complexes formed by reactions of laser-ablated group 3 metal atoms with methyl halides.

Abstract: Reactions of laser-ablated group 3 metal atoms with methyl halides have been carried out in excess of Ar during condensation and the matrix infrared spectra studied. The metals are as effective as other early transition metals in providing insertion products (CH3-MX) and higher oxidation state methylidene complexes (CH2-MHX) (X = F, Cl, Br) following alpha-hydrogen migration. Unlike the cases of the group 4-6 metals, the calculated methylidene complex structures show little evidence for agostic distortion, consistent with the previously studied group 3 metal methylidene hydrides, and the C-M bond lengths of the insertion and methylidene complexes are comparable to each other. However, the C-Sc bond lengths are 0.013, 0.025, and 0.029 A shorter for the CH2-ScHX complexes, respectively, and the spin densities are consistent with weak C(2p)-Sc(3d) pi bonding. The present results reconfirm that the number of valence electrons on the metal is important for agostic interaction in simple methylidene complexes.

Matrix Infrared Spectra and Quasirelativistic DFT Studies of ThS and ThS2

Abstract: Laser-ablated thorium atoms react with discharged sulfur vapor during co-condensation in excess argon at 7 K. The ThS fundamental is observed at 474.7 cm-1, and the ν1 and ν3 modes for ThS2 are observed at 451.4 and 431.5 cm-1, respectively, based on sulfur-34 substitution and infrared spectra of sulfur 32, 34 mixtures. Sulfur isotopic ν3 vibrational frequencies for ThS2 indicate a 112 ± 5° upper limit for the S−Th−S bond angle. Quasirelativistic DFT calculations performed on ThS and ThS2 find that ThS has the 1Σ+ ground state, and ThS2 has the 1A1 ground state with a bond angle of 111.6°. Calculated vibrational frequencies are in excellent agreement with the observed values, and support this first identification of molecular thorium sulfides.

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