: 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

Introduction to Surface Chemistry and Catalysis

CO2 hydrogenation for the acquisition of value-added chemicals is an economical means to deal with the CO2-relevant environmental problems, among which CO2 reduction to CH4 is an excellent model reaction for investigating the initial steps of CO2 hydrogenation. For the supported catalysts commonly used in such reactions, the tailoring of the interfacial effect between metal centers and supporting materials so as to obtain superior low-temperature CO2 methanation performance is a significant but challenging subject. In this work, we altered the size regimes of the Ru deposits in Ru/CeO2 assemblies and uncovered the competitive relationship between the strong metal–support interactions (SMSI) and the H-spillover effect in determining the methanation activities by some ex situ and in situ spectroscopic techniques coupled with density functional theory (DFT) calculations. For CeO2 nanowire supported single Ru atoms, Ru nanoclusters (ca. 1.2 nm in size), and large Ru nanoparticles (ca. 4.0 nm in size), the nan...

Low-Temperature CO2 Methanation over CeO2-Supported Ru Single Atoms, Nanoclusters, and Nanoparticles Competitively Tuned by Strong Metal–Support Interactions and H-Spillover Effect

Woody Plants of Ghana and Their Uses@@@Woody Plants of Ghana, with Special Reference to Their Uses

The projection of the eigenfunctions obtained in standard plane-wave first-principle electronic-structure calculations into atomic-orbital basis sets is proposed as a formal and practical link between the methods based on plane waves and the ones based on atomic orbitals. Given a candidate atomic basis, ({\it i}) its quality is evaluated by its projection into the plane-wave eigenfunctions, ({\it ii}) it is optimized by maximizing that projection, ({\it iii}) the associated tight-binding Hamiltonian and energy bands are obtained, and ({\it iv}) population analysis is performed in a natural way. The proposed method replaces the traditional trial-and-error procedures of finding appropriate atomic bases and the fitting of bands to obtain tight-binding Hamiltonians. Test calculations of some zincblende semiconductors are presented.

https://arxiv.org/pdf/cond-mat/9505075.pdf

Projection of plane-wave calculations into atomic orbitals

DFT mechanistic study on tandem sequential [4 + 2]/[3 + 2] addition reaction of cyclooctatetraene with functionalized acetylenes and nitrile imines

The mechanistic pathways for the sequential tandem [4 + 2] / [3 + 2] versus [3 + 2] / [4 + 2] cycloaddition reaction of functionalized acetylenes with cyclopentadiene and dimethyl diazopropane for the formation of norbornene pyrazolines, employed in the synthesis of pharmaceutically relevant compounds, have been studied computationally with DFT at the M06-2X/6-31G(d) and M06-2X/6-31G(d,p) levels of theory. We have established that, in the reaction of the parent (unsubstituted) acetylene with cyclopentadiene and dimethyl diazopropane, the order of the tandem addition has no substantial effects in product outcomes. The same product is obtained provided the reaction components remain the same for both [4 + 2]/[3 + 2] and [3 + 2]/[4 + 2] tandem addition sequences. The results indicate that the [4 + 2] Diels–Alder addition step is the rate-determining step irrespective of the addition order, while the 1,3-dipolar cycloaddition step has been found to generally proceed rapidly with very low activation energies. It has also been realized that the regio-, stereo-, and chemo-selectivities of the reaction are strictly dictated by the type of substituent on the parent acetylene. For substituted acetylenes, we conclude that the sequence of the tandem addition generally affects the type of isomeric product obtained. The [4 + 2]/[3 + 2] tandem addition sequence has been established to favor the exo stereo-selective isomer over the endo, whereas the [3 + 2]/[4 + 2] tandem addition sequence generally favors the endo product formation. Therefore, it is settled that the mechanistic route taken by any substrate in the [4 + 2]/[3 + 2] versus [3 + 2]/[4 + 2] sequential tandem cycloaddition is greatly affected by both electronic and steric factors. Electrophilicity indices calculations agree with the activation barriers obtained. Perturbation molecular orbital theory was employed to rationalize the results. Global reactivity indices calculations gave a good correlation with the activation energies.

Computational studies on [4 + 2] / [3 + 2] tandem sequential cycloaddition reactions of functionalized acetylenes with cyclopentadiene and diazoalkane for the formation of norbornene pyrazolines.

The ABO3 perovskite lanthanum ferrite (LaFeO3) is a technologically important electrode material for nickel-metal hydride batteries, energy storage and catalysis. However, the electrochemical hydrogen adsorption mechanism on LaFeO3 surfaces remains under debate. In the present study, we have employed spin-polarized density functional theory calculations, with the Hubbard U correction (DFT+U), to unravel the adsorption mechanism of H2 on the LaFeO3 (010) surface. We show from our calculated adsorption energies that the preferred site for H2 adsorption is the Fe-O bridge site, with an adsorption energy of −1.178 eV (including the zero point energy), which resulted in the formation of FeOH and FeH surface species. H2 adsorption at the surface oxygen resulted in the formation of a water molecule, which leaves the surface to create an oxygen vacancy. The H2 molecule is found to interact weakly with the Fe and La sites, where it is only physisorbed. The electronic structures of the surface-adsorption systems are discussed via projected density of state and Lowdin population analyses. The implications of the calculated adsorption strengths and structures are discussed in terms of the improved design of nickel–metal hydride (Ni–MH) battery prototypes based on LaFeO3.

/pdf/a-dft-u-investigation-of-hydrogen-adsorption-on-the-lafeo3-31ylfoyuwp.pdf

A DFT+U investigation of hydrogen adsorption on the LaFeO3(010) surface

The mechanisms of the tandem sequential [4 + 2]/[3 + 2] and [3 + 2]/[4 + 2] cycloaddition sequences involving an ester, cyclooctatetraene (COTE), and cyclic and acyclic nitrones for the formation of a diverse range of isoxazolidine derivatives and other synthetic precursors are reported. A thorough exploration of the PES has characterized several regio-, stereo- and enantio-selective mechanistic channels involved in these reactions. A perturbation molecular orbital (PMO) analysis been employed to rationalize the results. It has also been found that the initial electrocyclic ring closure of the COTE is the rate-determining step in the tandem sequential [4 + 2]/[3 + 2] addition sequence. The thermolytic breakdown of the tandem adducts to subsequent monocyclic, bicyclic and tricyclic adducts occurs generally with very high activation barriers making it an inconvenient synthetic approach. The different reactivity of all the three double bonds present in the dipolarophile is reported. Finally, the mechanistic possibilities of [3 + 2]/[4 + 2] addition sequences involving the same reaction components in the case of cyclic and acyclic nitrones are explored extensively. The results suggest a novel and convenient routes for obtaining products of high selectivity with less energetic requirements. In some instances, new cycloadducts hitherto unreported are obtained.

Quantum chemical studies on the mechanistic aspects of tandem sequential cycloaddition reactions of cyclooctatetraene with ester and nitrones

The pathways for the transition metal-assisted formation of 1,2-dinitrosoalkane complexes of cobalt and its congeners, have been studied using DFT/M06 with the basis set. The activation barriers for the one-step [3 + 2] addition pathway for the formation of 1,2-dinitrosoalkanes, proposed by Bergman and Becker, are generally low compared to the activation barriers for the [2 + 2] addition to form an intermediate, which is the first of the two-step pathway proposed by Rappe and Upton, which are very high. The barriers of the rearrangement of the Rappe intermediates to the final products by reductive elimination involving the second metal-nitrogen π-bond are also very high. The reactions of the Co complexes have lower activation barriers than Rh and Ir complexes. The barriers of the reactions involving olefins with electron-donating groups are generally lower compared to the reactions of the parent (unsubstituted) ethylene while the activation barriers for reactions of olefins with electron-withdrawing groups are generally higher compared to the parent (unsubstituted) ethylene. The one-step [3 + 2] pathway remains the most favoured irrespective of the metal centre or the nature of the olefin. The mechanism of the reaction is therefore settled in favour of the [3 + 2] addition pathway.

/pdf/3-2-versus-2-2-addition-a-density-functional-theory-study-on-346or9d2y7.pdf

[3 + 2] versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition Metal-Assisted Formation of 1,2-Dinitrosoalkanes

Evans Adei

Papers

DFT mechanistic study on tandem sequential [4 + 2]/[3 + 2] addition reaction of cyclooctatetraene with functionalized acetylenes and nitrile imines

Computational studies on [4 + 2] / [3 + 2] tandem sequential cycloaddition reactions of functionalized acetylenes with cyclopentadiene and diazoalkane for the formation of norbornene pyrazolines.

A DFT+U investigation of hydrogen adsorption on the LaFeO3(010) surface

Quantum chemical studies on the mechanistic aspects of tandem sequential cycloaddition reactions of cyclooctatetraene with ester and nitrones

[3 + 2] versus [2 + 2] Addition: A Density Functional Theory Study on the Mechanistic Aspects of Transition Metal-Assisted Formation of 1,2-Dinitrosoalkanes