Calculation of accurate imaginary frequencies and tunnelling coefficients for hydrogen abstraction reactions using IRCmax

The effect of level of theory on the imaginary frequency and corresponding tunnelling coefficients has been studied for a test set of hydrogen abstraction reactions: ?CH₂X + CH₃Y → CH₃X + ?CH₂Y for (X,Y) = (H,H), (H,CN), (H,F), (H,Li) and (F,Li). It is found that the imaginary frequency is very sensitive to the level of theory used, with Hartree-Fock (HF) methods severely overestimating the imaginary frequency compared with high-level CCSD(T)/6-311G(d,p) calculations. The errors for the other methods are smaller but nonetheless significant, with MP2 methods overestimating the imaginary frequency and density functional theory (DFT) methods underestimating it. In the case of the HF methods, this leads to errors in the tunnelling coefficient of several orders of magnitude, while for the better DFT and MP2 methods errors of a factor of 2–3 are observed. To address this problem, an IRCmax procedure for estimating the imaginary frequency has been developed and it is found that IRCmax imaginary frequencies calculated with CCSD(T)/6-311G(d,p) single points along a low-level HF/6-31G(d) minimum energy path provide excellent approximations to the high-level values, at a fraction of the computational cost.     

MULTISPECIES MODELING FOR ADAPTIVE MANAGEMENT OF HORSESHOE CRABS AND RED KNOTS IN THE DELAWARE BAY

Abstract Adaptive management requires that predictive models be explicit and transparent to improve decisions by comparing management actions, directing further research and monitoring, and facilitating learning. The rufa subspecies of red knots (Calidris canutus rufa), which has recently exhibited steep population declines, relies on horseshoe crab (Limulus polyphemus) eggs as their primary food source during stopover in Delaware Bay during spring migration. We present a model with two different parameterizations for use in the adaptive management of horseshoe crab harvests in the Delaware Bay that links red knot mass gain, annual survival, and fecundity to horseshoe crab dynamics. The models reflect prevailing hypotheses regarding ecological links between these two species. When reported crab harvest from 1998 to 2008 was applied, projections corresponded to the observed red knot population abundances depending on strengths of the demographic relationship between these species. We compared different simulated horseshoe crab harvest strategies to evaluate whether, given this model, horseshoe crab harvest management can affect red knot conservation and found that restricting harvest can benefit red knot populations. Our model is the first to explicitly and quantitatively link these two species and will be used within an adaptive management framework to manage the Delaware Bay system and learn more about the specific nature of the linkage between the two species.