New Directions in Consumer Behaviour Research

Consumer behaviour remains an evolving and fascinating area of research. In this article we highlight some of the current work by Canadian researchers in the areas of enhancing both the quality and application of consumer analysis. The work described below touches upon areas in which not just economic theory and methods, but also the policy process can be improved. The working papers cited here were all presented as part of the principal paper session, “What’s Going on in Consumer Behaviour?†held at the joint meeting of the Canadian Agricultural Economics Society and the Northeastern Agricultural and Resource Economics Association in Halifax, Nova Scotia in June 2004.Food Consumption/Nutrition/Food Safety, Marketing, Research Methods/ Statistical Methods,

Density Functional Theory and Molecular Dynamics Studies on Energetics and Kinetics for Electro-Active Polymers: PVDF and P(VDF-TrFE)

We use first principles methods to study static and dynamical mechanical properties of the ferroelectric polymer Poly(vinylidene fluoride) (PVDF) and its copolymer with trifluoro ethylene (TrFE). We use density functional theory [within the generalized gradient approximation (DFT-GGA)] to calculate structures and energetics for various crystalline phases for PVDF and P(VDF-TrFE). We find that the lowest energy phase for PVDF is a non-polar crystal with a combination of trans (T) and gauche (G) bonds; in the case of the copolymer the role of the extra (bulkier) F atoms is to stabilize T bonds. This leads to the higher crystallinity and piezoelectricity observed experimentally. Using the MSXX first principles-based force field (FF) with molecular dynamics (MD), we find that the energy barrier necessary to nucleate a kink (gauche pairs separated by trans bonds) in an all-T crystal is much lower (14.9 kcal/mol) in P(VDF-TrFE) copolymer than in PVDF (24.8 kcal/mol). This correlates with the observation that the polar phase of the copolymer exhibits a solid-solid a transition to a non-polar phase under heating while PVDF directly melts. We also studied the mobility of an interface between a polar and non-polar phases under uniaxial stress; we find a lower threshold stress and a higher mobility in the copolymer as compared with PVDF. Finally, considering plastic deformation under applied shear, we find that the chains for P(VDF-TrFE) have a very low resistance to sliding, particularly along the chain direction. The atomistic characterization of these "unit mechanisms" provides essential input to mesoscopic or macroscopic models of electro-active polymers.Comment: 15 pages 9 figures Electro-active polyme

Free energy and surface tension of arbitrarily large Mackay icosahedral clusters

We present a model for predicting the free energy of arbitrarily large Mackay icosahedral clusters. van der Waals clusters are experimentally observed to be particularly stable at magic numbers corresponding to these structures. Explicit calculations on the vibrational states were used to determine the spectrum of fundamental frequencies for smaller (~561 atoms). Combining these predictions with correlations for the moment of inertia and for the minimum potential energy of large clusters leads to free energies of arbitrary large clusters. The free energies are used to predict the chemical potential and surface tension as a function of size and temperature. This connects macroscopic properties to the microscopic atomic parameters

The hindered rotor density-of-states interpolation function

We construct an approximation to the partition function for hindered rotors based entirely on their asymptotic behavior and no fitting parameters. The approximant is shown to be quite accurate in all temperature ranges. Explicit auxiliary functions are derived for the Helmholtz free energy, internal energy, heat capacity, and entropy. We apply this function to estimating the heat capacity and unimolecular dissociation rate for ethane

Thermodynamic properties and homogeneous nucleation rates for surface-melted physical clusters

We predict the free energy of van der Waals clusters (Fn) in the surface-melted temperature regime. These free energies are used to predict the bulk chemical potential, surface tension, Tolman length, and vapor pressure of noble gas crystals. Together, these estimates allow us to make definitive tests of the capillarity approximation in classical homogeneous nucleation theory. We find that the capillarity approximation underestimates the nucleation rate by thirty orders of magnitude for argon. The best available experiments are consistent with our calculation of nucleation rate as a function of temperature and pressure. We suggest experimental conditions appropriate for determining quantitative nucleation rates which would be invaluable in guiding further development of the theory. To make the predictions of Fn, we develop the Shellwise Lattice Search (SLS) algorithm to identify isomer fragments and the Linear Group Contribution (LGC) method to estimate the energy of isomers composed of those fragments. Together, SLS/LGC approximates the distribution of isomers which contribute to the configurational partition function (for up to 147-atom clusters). Estimates of the remaining free energy contributions come from a previous paper in this series