"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

Blue-Shifting Hydrogen Bonds.

The nature and characteristics of the CH/π interaction are discussed by comparison with other weak molecular forces such as the CH/O and OH/π interaction. The CH/π interaction is a kind of hydrogen bond operating between a soft acid CH and a soft base π-system (double and triple bonds, C6 and C5 aromatic rings, heteroaromatics, convex surfaces of fullerenes and nanotubes). The consequences of CH/π hydrogen bonds in supramolecular chemistry are reviewed on grounds of recent crystallographic findings and database analyses. The topics include intramolecular interactions, crystal packing (organic and organometallic compounds), host/guest complexes (cavity-type inclusion compounds of cyclodextrins and synthetic macrocyclic hosts such as calixarenes, catenanes, rotaxanes and pseudorotaxanes), lattice-inclusion type clathrates (including liquid crystals, porphyrin derivatives, cyclopentadienyl compounds and C60 fullerenes), enantioselective clathrate formation, catalytic enantioface discriminating reactions and solid-state photoreaction. The implications of the CH/π concept for crystal engineering and drug design are evident.

CH/π hydrogen bonds in crystals

A systematic series of calculations encompassing a wide range of basis sets and correlated methods has been used to estimate the complete basis set, full CI hydrogen bond strength in the water dimer system. The largest basis set included up through h polarization functions on oxygen and g functions on hydrogen. The complete basis set limit for the self‐consistent‐field (SCF) interaction energy is estimated to be −3.55 kcal/mol with an accompanying correlation contribution of ∼−1.5 kcal/mol. This leads to an interaction energy of −5.1 kcal/mol, exclusive of vibrational zero‐point considerations, and is in good agreement with experimental measurements of −5.4±0.7 kcal/mol. Inclusion of an approximate adjustment for the basis set superposition error via the Boys/Bernardi counterpoise correction was found to substantially improve agreement with ΔE∞, our estimate of the complete basis set interaction energy, at the both the SCF and correlated levels for basis sets that were lacking in sufficient near‐valence d...

Application of systematic sequences of wave functions to the water dimer

Halogen Bonding in Supramolecular Chemistry.

Vibrational spectra of phenol are calculated with ab initio Hartree−Fock and MP2 methods as well as with density functional theory (DFT) using the 6-31G(d,p) basis set. A clear-cut assignment of th...

Density Functional, Hartree−Fock, and MP2 Studies on the Vibrational Spectrum of Phenol

Weak metal−arene interactions have been investigated in Zn, Cd, Hg, and Ni complexes of meso-tetraaryl m- and p-benziporphyrin (1 and 2) and of the new compound, m-benziporphodimethene (3). Compounds 1−3 incorporate the phenylene moiety into a macrocyclic structure so as to facilitate the interaction between the arene and coordinated metal ion. X-ray studies performed on Cd(II) and Ni(II) complexes show that the arene fragment approaches the ion at a distance much shorter than the sum of van der Waals radii. In chloronickel(II) m-benziporphyrin, a weak agostic bond is actually formed. In the NMR spectra of the Cd(II) and Hg(II) species, unusual 1H−M and 13C−M scalar couplings have been observed that are transmitted directly between the metal and the arene. DFT calculations performed for two Cd(II) species and subsequent AIM analysis show that the accumulation of electron density between the metal and arene necessary to induce these couplings is fairly small and the interaction is steric in nature. In the ...

Cadmium(II) and Nickel(II) Complexes of Benziporphyrins. A Study of Weak Intramolecular Metal−Arene Interactions

Systematic studies of the ability of a broad family of density functional methods applied to hydrogen‐bonded complexes have been carried out on the hydrogen fluoride dimer Specifically, calculations have been performed using basis sets of triple‐zeta quality with diffuse functions and multiple sets of polarization functions Various local and nonlocal exchange‐correlation functionals have been applied in order to study the structure, energetics, and vibrational properties of the hydrogen fluoride dimer The comparison with the experimental data, and also with results coming from ab initio methods (Hartree–Fock, Mo/ller–Plesset second order, and quadratic configuration interaction with the single and double excitations) shows good performance of nonlocal density functional methods for the description of hydrogen‐bonded systems The calculated binding energy, with nonlocal Becke exchange and Lee–Yang–Parr correlation functionals and a 6‐311++G(3df,3pd) basis set, is 448 kcal/mol and is in good agreement with experimental value and prior calculations

Application of density functional methods for the study of hydrogen‐bonded systems: The hydrogen fluoride dimer

The title complexes are studied by ab initio methods using double-ζ basis sets augmented by diffuse sp and two sets of polarization functions The binding energies decrease in the order (HF) 2 > HF…HCl > (HCl) 2 , all of which form pseudolinear H bonds While not important for (HF) 2 , correlation plays an increasingly larger role as each HF is replaced by HCl, contributing 2 3 of the total binding energy of (HCl) 2  (HF) 3 and (HCl) 3 are both C 3h cyclic and exhibit cooperativity, particularly (HF) 3 ; correlation appears to be negligible in the three-body nonadditive interaction energies The red shift of the HF stretch in (HF) 3 is nearly twice as great as in the dimer while little enhancement is observed in the HCl analogues The other two observable bands in the trimers are of fairly high intensity and correspond to an out-of-plane and in-plane bend The intermolecular stretching modes in the dimers and trimers are of very low intensity A clear relationship is noted between the intermolecular frequencies and the strength of the interaction

Structure, Energetics, and Vibrational Spectra of H-Bonded Systems. Dimers and Trimers of HF and HCl

The harmonic vibrational frequencies and infrared intensities of p-nitrophenol as well as geometries of ortho- and para-nitrophenol, are calculated with density functional theory (DFT), using BLYP functional and 6-31G(d,p) basis set. The calculated (unscaled) spectra are in very good agreement with the gas phase and solid IR spectra of p-nitrophenol. A detailed interpretation of the infrared spectra of p-nitrophenol is reported on the basis of the calculated potential energy distribution (PED). Several reassignments have been made.

Zdzisław Latajka

Papers

Density Functional, Hartree−Fock, and MP2 Studies on the Vibrational Spectrum of Phenol

Cadmium(II) and Nickel(II) Complexes of Benziporphyrins. A Study of Weak Intramolecular Metal−Arene Interactions

Application of density functional methods for the study of hydrogen‐bonded systems: The hydrogen fluoride dimer

Structure, Energetics, and Vibrational Spectra of H-Bonded Systems. Dimers and Trimers of HF and HCl

Theoretical infrared spectrum and revised assignment for para-nitrophenol. Density functional theory studies