"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

Matrix photoionization of methyl halides. Ultraviolet spectra of the parent cations and infrared evidence for intramolecular hydrogen-bonded parent anions in solid argon

The reactions of laser-ablated late lanthanide atoms and methanol were studied using matrix isolation infrared spectroscopy and electronic structure calculations at the density functional theory level. Both terbium and lutetium atoms react with methanol spontaneously to form the CH3OTbH and CH3OLuH insertion products, which react further with another methanol molecule to give the Tb(OCH3)2 and Lu(OCH3)2 products as found previously for uranium. The reactions of Dy through Yb and methanol first produce Ln(CH3OH) complexes during sample annealing, which isomerize to the CH3OLnH insertion products on visible irradiation. The Ln–H stretching frequencies of the CH3OLnH molecules exhibit a unique trend from Tb to Lu, which is also reproduced by theoretical calculations at the B3LYP level of theory. Although the CH3LnOH molecules are predicted to be more stable than the O–H bond insertion products, formation of the C–O bond insertion isomers is kinetically prohibited as revealed by calculated potential energy su...

Reactions of Late Lanthanide Metal Atoms and Methanol in Solid Argon: A Matrix Isolation Infrared Spectroscopic and Theoretical Study

Reactions of laser-ablated Y and La atoms with H2O2 gives the M(OH)2 and M(OH)3 molecules and the HOMO dehydration product, and the cation M(OH)2+ in solid argon. Density functional calculations show that the dihydroxide molecules and cations are bent at the metal center, and the symmetric and antisymmetric O−H stretching modes are both observed in the infrared spectra. The trihydroxide molecules have calculated C3h structures characterized by strong antisymmetric O−H and M−O stretching modes. Mulliken charges increase for all product molecules going down the Group 3 family and increase as one, two, and three OH ligands are bonded to the metal center. Evidence is also presented for the Y(OH)4- anion.

Infrared spectra and density functional calculations for M(OH)(2,3) and HOMO molecules and M(OH)2+ cations (M = Y, La).

This paper comprises the final section of a two-part study of the small nitride molecules and simple dinitrogen complexes of the lanthanide metals, except promethium. Simple nitrides of the general formulas LnN and (LnN)2 have been identified for Ln = Tb, Dy, Ho, Er, Tm, Yb, and Lu. Further elucidation of the Ln(N2) and Ln(NN)2 complexes is presented. The evidence supports the anticipated conclusion that the later lanthanide metals are less prone to dinitrogen complexation and that the nitrides of the later lanthanide metals require fewer dinitrogen units to achieve saturation.

Characterization of the Reaction Products of Laser-Ablated Late Lanthanide Metal Atoms with Dinitrogen. Matrix IR Spectra of LnN, (LnN)2, and Ln(NN)x Molecules

Lester Andrews

Papers

Matrix photoionization of methyl halides. Ultraviolet spectra of the parent cations and infrared evidence for intramolecular hydrogen-bonded parent anions in solid argon

Reactions of Late Lanthanide Metal Atoms and Methanol in Solid Argon: A Matrix Isolation Infrared Spectroscopic and Theoretical Study

Infrared spectra and density functional calculations for M(OH)(2,3) and HOMO molecules and M(OH)2+ cations (M = Y, La).

Characterization of the Reaction Products of Laser-Ablated Late Lanthanide Metal Atoms with Dinitrogen. Matrix IR Spectra of LnN, (LnN)2, and Ln(NN)x Molecules

Untersuchung von Goldfluoriden und ihren Edelgaskomplexen durch Matrixisolationsspektroskopie und quantenchemische Rechnungen