Ab initio thermochemistry and kinetics for carbon-centered radical addition and beta-scission reactions

A quantitative comparison of ab initio calculated rate coefficients using five computational methods and five different approaches of treating hindered internal rotation and tunneling with experimental values of rate coefficients for nine carbon-centered radical additions/beta scissions at 300, 600, and 1000 K is performed. The high-accuracy compound methods, CBS-QB3 and G3B3, and the density functionals, MPW1PW91, BB1K, and BMK, have been evaluated using the following approaches: (i) the harmonic oscillator approximation; (ii) the hindered internal rotor approximation for the internal rotation about the forming/breaking bond in the transition state and product; and the hindered internal rotation approximation combined with (iii) Wigner, (iv) Skodje and Truhlar, and (v) Eckart zero-curvature tunneling corrections. The density functional theory (DFT) based values for beta-scission rate coefficients deviate significantly from the experimental ones at 300 K, and the DFT methods do not accurately predict the equilibrium coefficient. The hindered rotor approximation offers a significant improvement in the agreement with experimental rate coefficients as compared to the harmonic oscillator treatment, especially at higher temperatures. Tunneling correction factors are smaller than 1.40 at 300 K and 1.03 at 1000 K. For both the CBS-QB3 method, including the hindered rotor treatment but excluding tunneling corrections, and the G3B3 method, including hindered rotor and Eckart tunneling corrections, a mean factor of deviation with experimentally observed values of 3 is found.     

Nonexistence results and estimates for some nonlinear elliptic problems

Here we study the local or global behaviour of the solutions of elliptic inequalities involving quasilinear operators of the type or . We give integral estimates and nonexistence results. They depend on properties of the supersolutions of the equationsL _A ^u=0,L _B ^v=0, which suppose weak coercivity conditions. Under stronger conditions, we give pointwise estimates in case of equalities, using Harnack properties.     

Interactive High-low Search: The Case of Lost Sales

We consider the problem of supplying perishable goods to disloyal customers. As in traditional stock-control literature, a penalty is incurred whenever there is a stockout. However, in contrast to mainstream models, loss of goodwill is explicitly treated by incorporating the behavioural assumption that a fixed proportion of unsatisfied demand is lost forever after each stockout. The problem consists of finding supply levels which minimize costs of over- and underproduction, given unknown but deterministic demand. We derive optimal adaptive search procedures under varying assumptions of a priori knowledge about demand. Optimal strategies are compared to myopic strategies. Our methodology extends the mathematical theory of ‘high-low search’ for a hidden point to incorporate the ‘Heisenberg principle’: the position of the hidden point (demand) is directly influenced by the actions (supply levels) of the searcher.     

Real-time detection of cofactor availability in genetically modified living Saccharomyces cerevisiae cells — Simultaneous probing of different geno- and phenotypes

This work describes a mediated amperometric method for simultaneous real-time probing of the NAD(P)H availability in two different phenotypes, fermentative and respiratory, of the phosphoglucose isomerase deletion mutant strain of S. cerevisiae, EBY44 [ENY.WA-1A pgi1-1D::URA3], and its parental strain, ENY.WA-1A. The developed method is based on multichannel detection using microelectrode arrays. Its versatility was demonstrated by using four microelectrode arrays for simultaneously monitoring the NAD(P)H availability of both geno- and phenotypes under the influence of two different carbon sources, glucose and fructose, as well as the cytosolic and mitochondrial inhibitor and uncoupler, dicoumarol. The obtained results indicate that the method is capable of accurately and reproducibly (overall relative standard error of mean 3.2%) mapping the real-time responses of the cells with different genotype–phenotype combinations. The ENY.WA cells showed the same response to glucose and fructose when dicoumarol was used; fermentative cells indicated the presence of cytosolic inhibition and respiratory cells a net effect of mitochondrial uncoupling. EBY44 cells showed cytosolic inhibition with the exception of respiratory cells when fructose was used as carbon source.     

An Isobar-Surfaces Approach to Multidimensional Outlier-Proneness

The aim of this paper is to define and investigate outlier-proneness for multivariate distributions. This is done by using a concept of ordering multivariate data based on isobar-surfaces, which yields an analogy of the results to the univariate case.     

Ab initio reaction path analysis of benzene hydrogenation to cyclohexane on Pt(111)

First-principles density functional theory calculations were performed to obtain detailed insight into the mechanism of benzene hydrogenation over Pt(111). The results indicate that benzene hydrogenation follows a Horiuti-Polanyi scheme which involves the consecutive addition of hydrogen adatoms. A first-principles-based reaction path analysis indicates the presence of a dominant reaction path. Hydrogenation occurs preferentially in the meta position of a methylene group. Cyclohexadiene and cyclohexene are expected to be at best minor products, since they are not formed along the dominant reaction path. The only product that can desorb is cyclohexane. Along the dominant reaction path, two categories of activation energies are found: lower barriers at approximately 75 kJ/mol for the first three hydrogenation steps, and higher barriers of approximately 88 kJ/mol for steps four and six, where hydrogen can only add in the ortho position of two methylene groups. The highest barrier at 104 kJ/mol is calculated for the fifth hydrogenation step, which may potentially be the rate-determining step. The high barrier for this step is likely the result of a rather strong C-H...Pt interaction in the adsorbed reactant state (1,2,3,5-tetrahydrobenzene) which increases the barrier by approximately 15 kJ/mol. Benzene and hydrogen are thought to be the most-abundant reaction intermediates.     

Relative impatience determines preference between contract bargaining and repeated bargaining

In this paper we consider the effect of the `impatience ratio' I (of the worker discount factor to the firm discount factor) on the preferences of the players between two bargaining schemes in an asymmetric information wage bargaining context. The firm has private information about the worker's value and the worker makes wage demands. In the contact bargaining scheme, a wage demand which is accepted in one period is binding for all future periods (and hence the bargaining ends after acceptance of a wage demand). In the repeated bargaining scheme, the parties continue to bargain irrespective of whether the worker has been hired or not, and any accepted wage demand is only valid for the period in which it was accepted. We establish the following results under the assumption that the worker's value is uniformly distributed on an interval: When the firm is more patient than the worker (I<1) both parties prefer contract bargaining, and when the worker is more patient than the firm (I >1) both prefer repeated bargaining. For any value of I, the preferred type of bargaining gives the lower unemployment.  The work of Bae has already shown that when players are equally patient (I=1) the players are indifferent between the two schemes, regardless of the distribution of the worker's value. This paper shows that Bae's indifference result (Bae, 1991) cannot be extended to unequally patient players. Received: December 1996/Final version: October 1998