Using molecular similarity to construct accurate semiempirical electron structure theories

Ab initio electronic structure methods give accurate results for small systems, but do not scale well to large systems. Chemical insight tells us that molecular functional groups will behave approximately the same way in all molecules, large or small. This molecular similarity is exploited in semiempirical methods, which couple simple electronic structure theories with parameters for the transferable characteristics of functional groups. We propse that high-level calculations on small molecules provide a rich source of parametrization data. In principle, we can select a functional group, generate a large amount of ab initio data on the group in various small-molecule environments, and "mine" this data to build a sophisticated model for the group's behavior in large molecules. This work details such a model for electron correlation: a semiempirical, subsystem-based correlation functional that predicts a subsystem's two-electron density as a functional of its one-electron density. This model is demonstrated on two small systems: chains of linear, minimal-basis (H-H)5, treated as a sum of four overlapping (H-H)2 subsystems; and the aldehyde group of a set of HOC-R molecules. The results provide an initial demonstration of the feasibility of this approach.Comment: The following article appeared in the Journal of Chemical Physics, 121 (12), 5635-5645 (2004) and may be found at http://jcp.aip.org

Magnetic molecules created by hydrogenation of Polycyclic Aromatic Hydrocarbons

Present routes to produce magnetic organic-based materials adopt a common strategy: the use of magnetic species (atoms, polyradicals, etc.) as building blocks. We explore an alternative approach which consists of selective hydrogenation of Polycyclic Aromatic Hydrocarbons. Self-Consistent-Field (SCF) (Hartree-Fock and DFT) and multi-configurational (CISD and MCSCF) calculations on coronene and corannulene, both hexa-hydrogenated, show that the formation of stable high spin species is possible. The spin of the ground states is discussed in terms of the Hund rule and Lieb's theorem for bipartite lattices (alternant hydrocarbons in this case). This proposal opens a new door to magnetism in the organic world.Comment: 6 pages, 4 figures and 2 table

Application of an Ultralight Aircraft to Aerial Surveys of Kangaroos on Grazing Properties

A Drifter ultralight aircraft was used as a platform for line-transect aerial surveys of three species of kangaroo in the sheep rangelands south-east of Blackall and north of Longreach in central-western Queensland in winter 1993 and 1994. Favourable comparisons between the results of ultralight surveys and those made from a helicopter flying the same transects and foot surveys along another set of transects, all within a few days of the ultralight survey, confirmed the expectation we had that an ultralight would be a satisfactory and much cheaper vehicle for conducting aerial surveys of kangaroos. The comparisons are even more favourable when data for the three species surveyed are combined, pointing to a problem in species identification and underlining the importance of using only experienced observers for aerial survey of kangaroos, whatever the platform. The use of an ultralight aircraft could have particular value where a comparatively small area, such as an individual sheep or cattle property, is under consideration. In this paper, we present the numerical comparisons, along with an evaluation of the practicability of using this type of aircraft. We also describe a possible future scenario in which an accreditation process could see approved kangaroo surveyors undertaking property assessments by ultralight, under contract to graziers or other interested parties

A simplified picture for Pi electrons in conjugated polymers : from PPP Hamiltonian to an effective molecular crystal approach

An excitonic method proper to study conjugated oligomers and polymers is described and its applicability tested on the ground state and first excited states of trans-polyacetylene, taken as a model. From the Pariser-Parr-Pople Hamiltonian, we derive an effective Hamiltonian based on a local description of the polymer in term of monomers; the relevant electronic configurations are build on a small number of pertinent local excitations. The intuitive and simple microscopic physical picture given by our model supplement recent results, such as the Rice and Garstein ones. Depending of the parameters, the linear absorption appears dominated by an intense excitonic peak.Comment: 41 Pages, 6 postscript figure

Optical Absorption Study by Ab initio Downfolding Approach: Application to GaAs

We examine whether essence and quantitative aspects of electronic excitation spectra are correctly captured by an effective low-energy model constructed from an {\em ab initio} downfolding scheme. A global electronic structure is first calculated by {\em ab initio} density-functional calculations with the generalized gradient approximation. With the help of constrained density functional theory, the low-energy effective Hamiltonian for bands near the Fermi level is constructed by the downfolding procedure in the basis of maximally localized Wannier functions. The excited states of this low-energy effective Hamiltonian ascribed to an extended Hubbard model are calculated by using a low-energy solver. As the solver, we employ the Hartree-Fock approximation supplemented by the single-excitation configuration-interaction method considering electron-hole interactions. The present three-stage method is applied to GaAs, where eight bands are retained in the effective model after the downfolding. The resulting spectra well reproduce the experimental results, indicating that our downfolding scheme offers a satisfactory framework of the electronic structure calculation, particularly for the excitations and dynamics as well as for the ground state.Comment: 14 pages, 6 figures, and 1 tabl

Do harvest refuges buffer kangaroos against evolutionary responses to selective harvesting?

There is a wealth of literature documenting a directional change of body size in heavily harvested populations. Most of this work concentrates on aquatic systems, but terrestrial populations are equally at risk. This paper explores the capacity of harvest refuges to counteract potential effects of size-selective harvesting on the allele frequency,of populations. We constructed a stochastic, individual-based model parameterized with data on red kangaroos. Because we do not know which part of individual growth would change in the course of natural selection, we explored the effects of two alternative models of individual growth in which alleles affect either the growth rate or the maximum size. The model results show that size-selective harvesting can result in significantly smaller kangaroos for a given age when the entire population is subject to harvesting. In contrast, in scenarios that include dispersal from harvest refuges, the initial allele frequency remains virtually unchanged

Modelling the Spatial and Temporal Dynamics of Kangaroo Populations for Harvest Management: Final Report to the Department of Environment and Heritage, Canberra

For the past three years, university researchers (University of Queensland and University of New England), kangaroo managers (Queensland, New South Wales, South Australia and the Commonwealth) and Packer Tanning have been collaborating on a research project aimed at improving kangaroo management. The project has three broad aims: - Predict kangaroo numbers using rainfall or satellite imagery and other environmental data - Indirectly monitor kangaroo numbers and harvest rate using harvest statistics (e.g. sex ratio, carcass weight, catch-per-unit-effort) - Optimise survey methods, frequency and design The work has involved collating over 20 years of data in three states on kangaroo density from aerial surveys, harvest offtake, satellite imagery (greenness index or NDVI) and rainfall. Such a long time series of data covering vast areas has enabled models to be developed that should lead to improved kangaroo management. These models can be used to predict future kangaroo numbers, which should enable the frequency and intensity of expensive aerial surveys to be reduced. Better prediction of kangaroo distribution within management zones should also help quota and tag allocation. Rainfall and pasture conditions obviously influence changes in kangaroo numbers, but the relationships needed to be quantified. The sex ratio and average weight of carcasses vary regionally, for a variety of reasons. Most usefully for managers, these statistics track kangaroo density or harvest rate in some cases. Both harvest statistics and satellite imagery have the advantage of being regularly updated and a high spatial resolution, both shortcomings of broad-scale aerial survey. Aerial surveys have been conducted annually in the eastern states, which may not be the most efficient survey frequency. The optimal frequency can be identified by considering the risks of the population dropping to low density or rising to high density. These risks can be considered as costs to the kangaroo industry, graziers and to conservation, which must then be balanced. Risk can be reduced by increasing survey frequency or intensity, which is a cost to management, or reducing harvest rate, which is a cost to industry. In more arid, uncertain environments, regular surveys are required. However, in many of these areas, harvests are low and a reduced harvest rate is unlikely to be a cost to industry. The data also suggest a greater influence of movement on red kangaroo population dynamics than previously thought, with large areas experiencing rates of increase much higher than possible through birth and survival alone. This suggests movement needs to be considered when forecasting kangaroo density even at a regional (>10,000 square km) scale

Ab initio equilibrium constants for H2O–H2O and H2O–CO2

Ab initio 6‐31G** electronic structure calculations have been used to determine the minimum energy geometries and vibrational frequencies of molecular clusters of water and carbon dioxide. Application of statistical thermodynamics leads to theoretical equilibrium constants for gas phase dimerization of water and the formation of an adduct of carbon dioxide with water.The low energy vibrations of the clusters lead to much larger contributions to the vibrational partitioning of the energy than do the fundamental vibrations of the monomeric species. A new ‘‘Harmonic‐Morse’’ formula is derived to estimate anharmonicity from optimized harmonic frequencies and two additional values on the potential surface for each vibration. These ab initiocalculations of equilibrium constants are very close to recent measurements and fall within the range of values obtained by other methods. This no‐parameter treatment gives excellent agreement for the equilibrium of H2O–CO2 near the supercritical fluid range of CO2 and suggests that a ‘‘Theory of Significant Clusters’’ may be extended to a model of supercritical fluids which includes the effects of anharmonicity

Evidence for Excimer Photoexcitations in an Ordered {\pi}-Conjugated Polymer Film

We report pressure-dependent transient picosecond and continuous-wave photomodulation studies of disordered and ordered films of 2-methoxy-5-(2-ethylhexyloxy) poly(para-phenylenevinylene). Photoinduced absorption (PA) bands in the disordered film exhibit very weak pressure dependence and are assigned to intrachain excitons and polarons. In contrast, the ordered film exhibits two additional transient PA bands in the midinfrared that blueshift dramatically with pressure. Based on high-order configuration interaction calculations we ascribe the PA bands in the ordered film to excimers. Our work brings insight to the exciton binding energy in ordered films versus disordered films and solutions. The reduced exciton binding energy in ordered films is due to new energy states appearing below the continuum band threshold of the single strand.Comment: 5.5 pages, 5 figure