"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-ablated Os and Ru atoms react with CO2 molecules upon cocondensation in excess argon at 7 K and neon at 4 K. Besides the dominant neutral products [OMCO, O2MCO (M = Os, Ru), O2Os(CO)2, and OCRu(O2)CO], anionic species [OMCO- (M = Os, Ru)] are also formed and identified through annealing, ultraviolet irradiation, isotopic substitution, and CCl4-doping experiments. DFT calculations have been performed on possible products, and the overall agreement between the calculated and observed vibrational absorptions supports the product identifications.

Reactions of Laser-Ablated Osmium and Ruthenium Atoms with Carbon Dioxide: Matrix Infrared Spectra and Density Functional Calculations on OMCO, O2MCO, OMCO- (M = Os, Ru), O2Os(CO)2, and OCRu(O2)CO

Cocondensation reaction between phosphine and fluorine: matrix infrared spectra of difluorophosphorane, difluorophosphine and fluorophosphine

Atomic mercury in solid hydrogen reacts when subjected to mercury arc irradiation to form the linear HgH2 molecule with strong IR absorptions at 1902.3 and 772.8 cm−1. Annealing leads to HgH2 dimer and trimer and warming above 7 K allows hydrogen to sublime and solid HgH2 to form. This covalent molecular solid is characterized by strong IR absorptions at 1802, 739 and 673 cm−1 and by decomposition at 150–170 K. Solid para-hydrogen gives sharper HgH2 absorptions at 1905.8 and 774.3 cm−1 and forms a more amorphous HgH2 solid with bands at 1813, 741 and 683 cm−1.

Mercury dihydride forms a covalent molecular solid

Matrix infrared study of the neodymium-doped yttrium aluminum garnet laser depolymerization products of solid phosphorus oxide (P4O10)

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2+ cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and 18O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2+ cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most o...

Lester Andrews

Papers

Reactions of Laser-Ablated Osmium and Ruthenium Atoms with Carbon Dioxide: Matrix Infrared Spectra and Density Functional Calculations on OMCO, O2MCO, OMCO- (M = Os, Ru), O2Os(CO)2, and OCRu(O2)CO

Cocondensation reaction between phosphine and fluorine: matrix infrared spectra of difluorophosphorane, difluorophosphine and fluorophosphine

Mercury dihydride forms a covalent molecular solid

Matrix infrared study of the neodymium-doped yttrium aluminum garnet laser depolymerization products of solid phosphorus oxide (P4O10)

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations