Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Investigation.

Knowledge of the relative stabilities of alane (AlH(3)) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for 38 alane complexes with NH(3-n)R(n) (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH(2-n)R(n) (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered.

Cobalt-porphyrin catalyzed electrochemical reduction of carbon dioxide in water. 2. Mechanism from first principles.

We apply first principles computational techniques to analyze the two-electron, multistep, electrochemical reduction of CO(2) to CO in water using cobalt porphyrin as a catalyst. Density functional theory calculations with hybrid functionals and dielectric continuum solvation are used to determine the steps at which electrons are added. This information is corroborated with ab initio molecular dynamics simulations in an explicit aqueous environment which reveal the critical role of water in stabilizing a key intermediate formed by CO(2) bound to cobalt.

Cobalt-porphyrin catalyzed electrochemical reduction of carbon dioxide in water. 1. A density functional study of intermediates.

The reduction of carbon dioxide by cobalt porphyrins is thought to be a multistep reaction with several possible intermediates and reaction pathways. We here investigate a number of possible intermediates in this reaction using density functional theory, including both hybrid (B3LYP) and pure (PBE and BP86) functionals. Optimum structures are located, and harmonic vibrational frequencies and thermal corrections are computed for the low-lying electronic states for all intermediates.

Utilizing high performance computing for chemistry: parallel computational chemistry.

Parallel hardware has become readily available to the computational chemistry research community. This perspective will review the current state of parallel computational chemistry software utilizing high-performance parallel computing platforms. Hardware and software trends and their effect on quantum chemistry methodologies, algorithms, and software development will also be discussed.

Elucidating the bimodal acid-base behavior of the water-silica interface from first principles.

Understanding the acid-base behavior of silica surfaces is critical for many nanoscience and bionano interface applications. Silanol groups (SiOH) on silica surfaces exhibit two acidity constants-one as acidic as vinegar-but their structural basis remains controversial. The atomic details of the more acidic silanol site govern not just the overall surface charge density at near neutral solution pH but also how ions and biomolecules interact with and bind to silica immersed in water.

Ab initio molecular dynamics study of carbon dioxide and bicarbonate hydration and the nucleophilic attack of hydroxide on CO2.

We apply ab initio molecular dynamics (AIMD) to study the hydration structures of the carbon dioxide molecule and the bicarbonate and carbonate anions in liquid water. We also compute the free energy change associated with the nucleophilic attack of the hydroxide ion on carbon dioxide. CO2 behaves like a hydrophobic species and exhibits weak interactions with water molecules.

Theoretical and experimental investigation of the thermochemistry of CrO2(OH)2(g).

In this paper, we report the results of equilibrium pressure measurements designed to identify the volatile species in the Cr-O-H system and to resolve some of the discrepancies in existing experimental data. In addition, ab initio calculations were performed to lend confidence to a theoretical approach for predicting the thermochemistry of chromium-containing compounds. Equilibrium pressure data for CrO2(OH)2 were measured by the transpiration technique for the reaction 0.

Local Møller-Plesset Perturbation Theory: A Massively Parallel Algorithm.

A massively parallel algorithm is presented for computation of energies with local second-order Møller-Plesset (LMP2) perturbation theory. Both the storage requirement and the computational time scale linearly with the molecular size. The parallel algorithm is designed to be scalable, employing a distributed data scheme for the two-electron integrals, avoiding communication bottlenecks, and distributing tasks in all computationally significant steps.

High-level ab initio thermochemical data for halides of chromium, manganese, and iron.

The thermochemistry of the transition-metal fluorides and chlorides MF(n)() and MCl(n)() (M = Cr, Mn, Fe; n = 1, 2) has been characterized by high-level ab initio electronic structure methods. Geometries and harmonic vibrational frequencies were computed at the B3LYP level of theory using triple-zeta basis sets including diffuse and polarization functions. Heats of formation were computed from isogyric reaction energies at the CCSD(T) level using high-quality basis sets, including corrections for core-valence correlation and scalar relativistic effects.

BAC-MP4 predictions of thermochemistry for gas-phase antimony compounds in the Sb-H-C-O-Cl system.

Calibrated by both experimental data and high-level coupled-cluster calculations, the BAC-MP4 methodology was applied to 51 SbL(n) (L = H, CH(3), C(2)H(5), Cl, and OH, n = 1-5) molecules, providing calculated heats of formation and associated thermodynamic parameters. These data identify a linear variation in heats of formation with ligand substitution, trends in bond dissociation energies (BDEs) with ligand identity [BDE(Sb-C(2)H(5)) < BDE(Sb-CH(3)) < BDE(Sb-H) < BDE(Sb-Cl) < BDE(Sb-OH)], and a monotonic decrease in BDE upon successive ligand elimination. The linear variation in BDE is consistent with the behavior of other group V elements, in contrast to the characteristic high-low-high trend of adjacent group III (In) and group IV (Sn) elements.

Thermochemistry of the chromium hydroxides Cr(OH)n, n = 2-6, and the oxyhydroxide CrO(OH)4: ab initio predictions.

We here present a high-level ab initio study of the thermochemistry of the chromium hydroxides Cr(OH)n, n = 2-6, and of the oxyhydroxide CrO(OH)4. Optimum geometries and harmonic vibrational frequencies were determined at the B3LYP level of theory using basis sets of triple-zeta quality including polarization and diffuse functions. Heats of formation were obtained from isogyric reaction energies computed at the CCSD(T) level of theory using large basis sets and including corrections for core-valence correlation, scalar relativistic effects, and basis set incompleteness.

BAC-MP4 predictions of thermochemistry for gas-phase indium compounds in the In-H-C-O-Cl system.

The BAC-MP4 methodology has been used to calculate the heats of formation and associated thermodynamic parameters for a family of 51 different one-, two-, and three-coordinate indium compounds. The ligands explored were H, CH3, C2H5, OH, OCH3, and Cl. The BAC-MP4 methodology was calibrated by both experimental data and high-level coupled-cluster calculations.