"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

One-photon and two-photon matrix photoionization experiments have been performed with substituted biphenyls, fluorene and 9,10-dihydrophenanthrene. Absorption spectra in the red region correlate with photoelectron spectra for a π3→π6 transition and indicate a relaxation of the dihedral angle upon ionization. Sharp ultraviolet absorption spectra are assigned to π→π* transitions for the matrix-isolated cations.

Absorption spectra of substituted biphenyl and related cations in solid argon and a comparison with photoelectron spectra

Codeposition of laser ablated boron atoms with a mixture of carbon disulfide in argon produced SBCS with absorption bands at 1201.9 and 1226.8 cm -1 for 11 B and 10 B, respectively. Carbon-13 substitution shifted these bands to 1188.2 and 1210.3 cm -1 . Sulfur-34 isotopic counterparts were observed at 1192.7 and 1217.6 cm -1 and scrambled isotopic sulfur revealed intermediate new bands at 1197.2, 1222.8, and 1221.8 cm -1 , respectively. Ab initio calculations of isotopic frequencies confirmed the identification of the SBCS insertion product

Laser ablated boron atom reaction with carbon disulfide: infrared spectrum of SBCS in solid argon and ab initio geometry and frequency calculations for possible products

Laser-ablated scandium, yttrium, and lanthanum atoms were reacted with CS2 and OCS molecules in an argon matrix. Products of the type SMCX and S−M(η2-CX) (X = S or O) were formed on sample deposition. Photolysis favored the S−M(η2-CX) complex, while annealing increased the more stable SMCX isomer. Product absorptions are identified by density-functional frequency calculations and isotopic substitutions. This work reports the first vibrational spectroscopic characterization of Sc, Y, and La reaction products with CS2 and OCS and the subsequent interconversion between SMCX and S−M(η2-CX) structural isomers.

Reactions of group 3 transition metal atoms with CS2 and OCS : Matrix isolation infrared spectra and density-functional calculations of SMCS, SM-(η2-CS), SMCO, and SM-(η2-CO) in solid argon

Lester Andrews

Papers

Absorption spectra of substituted biphenyl and related cations in solid argon and a comparison with photoelectron spectra

Laser ablated boron atom reaction with carbon disulfide: infrared spectrum of SBCS in solid argon and ab initio geometry and frequency calculations for possible products

Reactions of group 3 transition metal atoms with CS2 and OCS : Matrix isolation infrared spectra and density-functional calculations of SMCS, SM-(η2-CS), SMCO, and SM-(η2-CO) in solid argon

Spektroskopische Beobachtung eines Gruppe‐12‐Oxyfluorids: eine Matrixisolations‐ und quantenchemische Untersuchung von Quecksilberoxyfluoriden

Ultraviolet absorption spectra of all-trans-octatetraene and -decapentaene in solid argon