Ab initio effective potentials for use in molecular quantum mechanics

We have investigated the method of effective potentials for replacing the core electrons in molecular calculations. The effective potential has been formulated in a way which simplifies computations while producing wave functions of ab initio quality. The effective potential is expressed in an analytic form which (i) represents the actual ab initio nonlocal potential (as defined by the matrix elements for a given basis set) and (ii) permits efficient computations of the effective-potential integrals (by incorporating the properties of Gaussian basis functions). To minimize the number of basis functions required in the molecular calculations, we define a new ab initio effective potential derived from modified Hartree-Fock valence orbitals whose core character has been removed. The effective-potential method as formulated becomes a very strong and reliable tool in attempting calculations on very large molecules. Applications to Li, Na, and K are presented

Developing Poultry Facility Type Information from USDA Agricultural Census Data for Use in Epidemiological and Economic Models

The epidemiological and economic modeling of poultry diseases requires knowing the size, location, and operational type of each poultry type operation within the US. At the present time, the only national database of poultry operations that is available to the general public is the USDA's 2002 Agricultural Census data, published by the National Agricultural Statistics Service, herein referred to as the 'NASS data'. The NASS data provides census data at the county level on poultry operations for various operation types (i.e., layers, broilers, turkeys, ducks, geese). However, the number of farms and sizes of farms for the various types are not independent since some facilities have more than one type of operation. Furthermore, some data on the number of birds represents the number sold, which does not represent the number of birds present at any given time. In addition, any data tabulated by NASS that could identify numbers of birds or other data reported by an individual respondent is suppressed by NASS and coded with a 'D'. To be useful for epidemiological and economic modeling, the NASS data must be converted into a unique set of facility types (farms having similar operational characteristics). The unique set must not double count facilities or birds. At the same time, it must account for all the birds, including those for which the data has been suppressed. Therefore, several data processing steps are required to work back from the published NASS data to obtain a consistent database for individual poultry operations. This technical report documents data processing steps that were used to convert the NASS data into a national poultry facility database with twenty-six facility types (7 egg-laying, 6 broiler, 1 backyard, 3 turkey, and 9 others, representing ducks, geese, ostriches, emus, pigeons, pheasants, quail, game fowl breeders and 'other'). The process involves two major steps. The first step defines the rules used to estimate the data that is suppressed within the NASS database. The first step is similar to the first step used to estimate suppressed data for livestock [Melius et al (2006)]. The second step converts the NASS poultry types into the operational facility types used by the epidemiological and economic model. We also define two additional facility types for high and low risk poultry backyards, and an additional two facility types for live bird markets and swap meets. The distribution of these additional facility types among counties is based on US population census data. The algorithm defining the number of premises and the corresponding distribution among counties and the resulting premises density plots for the continental US are provided

Charge-transfer process using the molecular-wave-function approach: The asymmetric charge transfer and excitation in Li + Na+ and Na + Li+

The charge-transfer processes occurring in collisions of Li + Na+ and Na + Li+ have been studied theoretically using the molecular-wave-function approach. The wave functions and Born-Oppenheimer breakdown terms were evaluated using rigorous methods. The six lowest molecular states (dissociating to the 2s and 2p atomic states on Li and to the 3s and 3p atomic states of Na) were included in the coupled equations. The transition probabilities were calculated using linear trajectories for a variety of impact parameters and ion velocities. We find that the over-all transition processes are well represented as a succession of simple two-state transition processes (Σ-Σ, Σ-Π, and Π-Π). The Σ-Σ two-state process can be described in terms of three steps involving (i) a coupling region as the atoms come together [(10-20)a0], (ii) an uncoupled phase changing region for shorter separatons (<10a0), and (iii) a decoupling region as the atoms depart [(10-20)a0]. On the other hand, in the molecular—wave-function formulation, the Σ-Π two-state transition process involves continuous coupling (for R<7a0). As a result the transition probabilities for Σ-Π coupling differs from that of Σ-Σ coupling, leading to rather different forms for the cross sections

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

Knowledge of the relative stabilities of alane (AlH3) 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 thirty-eight alane complexes with NH3-nRn (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine, and obtaining upper limits of delta G for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. Based on this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.Comment: Accepted by the Journal of Physical Chemistry

Experimental and modeling studies of the micro-structures of opposed flow diffusion flames: Methane

The micro-structure of an atmospheric pressure, opposed flow, methane diffusion flame has been studied using heated micro-probe sampling and chemical kinetic modeling. Mole fraction profiles of major products as well as trace aromatic, substituted aromatic, and polycyclic aromatic hydrocarbons (PAH up to C{sub 16}H{sub 10}, e.g. pyrene) were quantified by direct gas chromatography/mass spectrometry (GC/MS) analysis of samples withdrawn from within the flame without any pre-concentration. Mole fractions range from 0.8 to 1.0 {times} 10{sup {minus}7}. The experimental measurements are compared to results from a newly-developed chemical kinetic model that includes chemistry for the production and consumption of aromatics and PAH species. The model predictions are in reasonable agreement with the experimental data for the major species profiles and for the peak concentrations of many of the trace aromatics and PAH species. 36 refs

Experimental and Modeling Investigation of Aromatic and Polycyclic Aromatic Hydrocarbon Formation in a Premixed Ethylene Flame

Experimental and detailed chemical kinetic modeling has been performed to investigate aromatic and polyaromatic hydrocarbon formation pathways in a rich, sooting, ethylene-oxygen-argon premixed flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.5 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer (GC/MS) technique. Measurements were made in the flame and post-flame zone for a number of low molecular weight species, aliphatics, aromatics and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-aromatic fused rings. The modeling results show the key reaction sequences leading to aromatic and polycyclic aromatic hydrocarbon growth involve the combination of resonantly stabilized radicals. In particular, propargyl and 1-methylallenyl combination reactions lead to benzene and methyl substituted benzene formation, while polycyclic aromatics are formed from cyclopentadienyl radicals and fused rings that have a shared C{sub 5} side structure. Naphthalene production through the reaction step of cyclopentadienyl self-combination and phenanthrene formation from indenyl and cyclopentadienyl combination were shown to be important in the flame modeling study. The removal of phenyl by O{sub 2} leading to cyclopentadienyl formation is expected to play a pivotal role in the PAH or soot precursor growth process under fuel-rich oxidation conditions