"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

This paper gives the 2010 self-consistent set of values of the basic constants and conversion factors of physics and chemistry recommended by the Committee on Data for Science and Technology (CODATA) for international use. The 2010 adjustment takes into account the data considered in the 2006 adjustment as well as the data that became available from 1 January 2007, after the closing date of that adjustment, until 31 December 2010, the closing date of the new adjustment. Further, it describes in detail the adjustment of the values of the constants, including the selection of the final set of input data based on the results of least-squares analyses. The 2010 set replaces the previously recommended 2006 CODATA set and may also be found on the World Wide Web at physics.nist.gov/constants.

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CODATA Recommended Values of the Fundamental Physical Constants: 2006

: 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

We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

Large-Scale Fabrication of Boron Nitride Nanosheets and Their Utilization in Polymeric Composites with Improved Thermal and Mechanical Properties

Structure, bonding, and magnetism of small Fen, Con, and Nin clusters, n ≤ 5

The vibrational spectra of the nucleic acid bases adenine, thymine, guanine, and cytosine are calculated in the frame of density functional theory .DFT . In particular we use the Kohn)Sham scheme with gradient corrections for exchange and correlation to determine normal modes, frequencies, and intensities. The DFT results are found to be in good agreement with the experiment. Our computations provide assignments for IR, Raman, and neutron inelastic scattering spectroscopies; yield characteristic vibrational fingerprints of each compound for its identification in larger systems; and show general vibrational trends of nucleic acids. The Kohn)Sham scheme is further applied to obtain the spectra of the Watson)Crick pairs adenine-thymine and guanine- cytosine. A large number of monomeric vibrations are recognized in dimers; characteristic vibrations of pairs, which are mainly attributed to hydrogen bridges, are quantified according to changes in normal modes and frequency shifts. Binding and zero-point vibrational energies are analyzed to establish the stability of the complexes and discuss the quality of the energetic calculations. Q 1999 John Wiley & Sons, Inc. J Comput Chem 20: 511)530, 1999

Vibrational spectra of nucleic acid bases and their Watson–Crick pair complexes

The structural and electronic properties of a series of imidazoline (I) derivatives R1-I-R2 have been studied by means of density functional theory. The chosen compounds have different chain lengths (R1) and pendant (R2) groups, where R1=CH3, (CH2)nCH3 (n=2,4,…,16) and R2=H, CH3, C2H5, C3H7, C2H5OH, C2H5NH2, C2H5SH, C2H5COOH, and C2H5Cl. All-electron calculations were carried out by means of the Gaussian-98 program. Natural and Mulliken population analysis were determined for each of the neutral and charged molecules. The reactivity was analyzed in terms of the Fukui indices. The results indicate a high reactivity for both the tertiary (showing the biggest) and the iminic nitrogen atoms of the imidazoline ring. Although the N site of the pending groups has a much lower reactivity, this is significantly increased when a sulfur atom replaces it. In general, the reactivity of the N atoms of the ring depends significantly on the substituents. As expected, the frontier molecular orbitals, highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), also describe the reactivity behavior. As the size of the R1 chain increases, the two N atoms of the ring increase their nucleophilic character, since the HOMOs become more highly located. The obtained results help to explain the observed increased activity of these derivatives when they are used as inhibitors of corrosion moieties on metallic surfaces. Finally, the solvent effects on the ground-state geometry were studied for one of the most promising reactive imidazolines; for which its interaction with an iron oxide surface was also addressed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001

Reactivity properties of derivatives of 2-imidazoline: an ab initio DFT study

In this paper first principles total energy calculations to study the adsorption of amine group (NH2) on graphene (G) and boron nitride (hBN) nanosheets are developed; the density functional theory, within the local density approximation and Perdew-Wang functional was employed. The sheets were modeled with a sufficiently proved CnHm-like cluster with armchair edge. The optimized geometry was obtained following the minimum energy criterion, searching on four positions for each nanosheet: perpendicular to the carbon atom, on the hexagon, inside the hexagon and on the bridge C–C, for the G-amine interaction; and, perpendicular to the B, perpendicular to the N, on the hexagon, and inside the hexagon, for the hBN-amine interaction. A physisorption, with amine parallel to the C–C–C bond with a distance graphene-amine of 2.56 A, was found. For the case of BN a B–N bond, with bond length equal to 1.56 A, was found; the amine lies perpendicular to the nanosheet. When the graphene is doped with B and Al atoms a chemisorption with B–N (1.57 A) and Al–N (1.78 A) bonds is observed; the bond angle in the amine group is also incremented, 5.5° and 8.1°, respectively. In the presence of point defects (monovacancies) of B in the hBN-amine and C in the G-amine, there exists chemisorption, increasing the reactivity of the sheets.

Miguel Castro

Papers

Structure, bonding, and magnetism of small Fen, Con, and Nin clusters, n ≤ 5

Vibrational spectra of nucleic acid bases and their Watson–Crick pair complexes

Reactivity properties of derivatives of 2-imidazoline: an ab initio DFT study

A density functional theory analysis for the adsorption of the amine group on graphene and boron nitride nanosheets

The role of the Jahn–Teller distortions on the structural, binding, and magnetic properties of small Fen clusters, n≤7