"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.

A Chemist's Guide to Density Functional Theory

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 density functional formalism, its applications and prospects

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.

The Halogen Bond

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...

Generation and Detection of Reactive Oxygen Species in Photocatalysis

: 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

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

Laser Raman matrix isolation studies of nitrogen dioxide. Resonance Raman spectrum of NO2 and Raman spectrum of N2O4

Infrared spectra and structures of lithium-benzene and lithium-dibenzene complexes in solid argon

Laser-ablated Mn and Re atoms and electrons react with CO upon co-condensation in excess argon and neon to produce carbonyl neutrals and anions. These species are identified through isotopic substitution, CCl4 doping to trap ablated electrons, and density functional theory isotopic frequency calculations. MnCO is identified at 1933.6 cm-1 in argon and at 1950.7 cm-1 in neon, which are in agreement with the gas phase 1955 ± 15 cm-1 photoelectron measurement. MnCO- is found at 1789.4 cm-1 in argon and 1807.5 cm-1 in neon. The Mn(CO)2 and Re(CO)2 dicarbonyls are major product absorptions. Annealing to allow further reaction of CO produces higher carbonyls including Mn2(CO)10 and Re2(CO)10 in solid argon. Argon and neon matrix experiments are compared for both metals.

Matrix Infrared Spectra and Density Functional Calculations of Manganese and Rhenium Carbonyl Neutral and Anion Complexes

Uranium atoms from pulsed Nd:YAG laser ablation of a uranium metal target were codeposited with carbon monoxide and carbon dioxide in excess argon at 10K. Infrared spectra following the U + CO reaction revealed strong new absorption bands at 804.4 and 852.6 cm[sup [minus]1], which are assigned to the CUO product on the basis of isotopic shifts, FG matrix calculations, and ab initio pseudopotential calculations. An absorption at 2027.5 cm[sup [minus]1] is attributed to the asymmetric secondary reaction product CU(O)CO. In both the U + Co and U + CO[sub 2] reactions, bands at 870.9 and 1963.8 cm[sup [minus]1] were observed and assigned to the association product of UO[sub 2] and CO. Lastly, in the U + CO[sub 2] experiments, new absorption band pairs were observed at 804.4 and 1799.6 cm[sup [minus]1] and at 801.5 and 2011.7 cm[sup [minus]1]. The former pair was almost destroyed on annealing and is assigned to the OUCO insertion product. The latter pair is attributed to an OCU(O)CO species. The direct reaction of U atoms with CO and CO[sub 2] requires an activation energy, which is provided by hyperthermal U atoms from pulsed laser evaporation. 25 refs., 5 figs., 2 tabs.

Matrix infrared spectra of the products of uranium-atom reactions with carbon monoxide and carbon dioxide

Reactions of zinc and cadmium atoms with ozone during condensation with excess nitrogen or argon produced B+O3− ion‐pairs having infrared, Raman, and optical spectra similar to the analogous alkali and alkaline earth metal species. Additional infrared and Raman evidence was found for a different B+O3− ion‐pair geometry. Mercury arc photolysis reduced ozonide absorptions and produced new 810 cm−1 zinc isotopic triplets which showed the appropriate 18O shifts for ZnO, and a new 719 cm−1 band which showed the proper 18O displacement for CdO. This nitrogen matrix work provides good measures of the yet‐to‐be‐observed gas‐phase fundamentals of these high temperature oxides.

Infrared, Raman, and visible spectroscopic studies of Zn and Cd matrix reactions with ozone. Spectra of metal ozonides and oxides in solid argon and nitrogen

Lester Andrews

Papers

Laser Raman matrix isolation studies of nitrogen dioxide. Resonance Raman spectrum of NO2 and Raman spectrum of N2O4

Infrared spectra and structures of lithium-benzene and lithium-dibenzene complexes in solid argon

Matrix Infrared Spectra and Density Functional Calculations of Manganese and Rhenium Carbonyl Neutral and Anion Complexes

Matrix infrared spectra of the products of uranium-atom reactions with carbon monoxide and carbon dioxide

Infrared, Raman, and visible spectroscopic studies of Zn and Cd matrix reactions with ozone. Spectra of metal ozonides and oxides in solid argon and nitrogen