Model studies of the optical rotation,and theoretical determination of its sign for β‐pinene and trans‐pinane

We have carried out extensive studies on the basis set dependence of the calculated specific optical rotation (OR) in molecules at the level of the time–dependent Hartree–Fock and density functional approximations. To reach the limits of the basis set saturation, we have devised an artificial model, the asymmetrically deformed (chiral) methane (CM) molecule. This small system permits to use basis sets which are prohibitively large for real chiral molecules and yet shows all the important features of the basis set dependence of the OR values. The convergence of the OR has been studied with n‐aug‐cc‐pVXZ basis sets of Dunning up to the 6–ζ. In a parallel series of calculations, we have used the recently developed large polarized (LPolX) basis sets. The relatively small LPolX sets have been shown to be competitive to very large n‐aug‐cc‐pVXZ basis sets. The conclusions reached in calculations of OR in CM concerning the usefulness of LPolX basis sets have been further tested on (S)‐methyloxirane and (S)‐fluoro‐oxirane. The smallest set of the LPolX family (LPol–ds) has been found to yield OR values of similar quality as those obtained with much larger Dunning's aug‐cc‐pVQZ basis set. These results have encouraged us to carry out the OR calculations with LPol–ds basis sets for systems as large as β‐pinene and trans‐pinane. In both cases, our calculations have lead to the correct sign of the OR value in these molecules. This makes the relatively small LPol–ds basis sets likely to be useful in OR calculations for large molecules. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Infinite horizon stopping problems with (nearly) total reward criteria

We study an infinite horizon optimal stopping Markov problem which is either undiscounted (total reward) or with a general Markovian discount rate. Using ergodic properties of the underlying Markov process, we establish the feasibility of the stopping problem and prove the existence of optimal and ε$\epsilon$-optimal stopping times. We show the continuity of the value function and its variational characterisation (in the viscosity sense) under different sets of assumptions satisfied by large classes of diffusion and jump–diffusion processes. In the case of a general discounted problem we relax a classical assumption that the discount rate is uniformly separated from zero.     

Self-approximation of Hurwitz zeta-functions with rational parameter

In this paper, we show the self-approximation property for Hurwitz zeta-functions with rational parameters. Namely, we prove that ζ(s?+?iατ, a/b) approximates uniformly ζ(s?+?iβτ, a/b) for infinitely many real τ , where α, β are arbitrary real numbers linearly independent over $ \mathbb{Q} $ , and s is in a compact set lying in the open right half of the critical strip.     

Holomorphic mappings preserving Minkowski functionals

We show that the equality _m1(f(x))=_m2(g(x))$m_1\left(f\left(x\right)\right)=m_2\left(g\left(x\right)\right)$ for x$x$ in a neighborhood of a point a$a$ remains valid for all x$x$ provided that f$f$ and g$g$ are open holomorphic maps, f(a)=g(a)=0$f\left(a\right)=g\left(a\right)=0$ and _m1,_m2$m_1,m_2$ are Minkowski functionals of bounded balanced domains. Moreover, a polynomial relation between f$f$ and g$g$ is obtained.     

On Hidden Markov Processes with Infinite Excess Entropy

We investigate stationary hidden Markov processes for which mutual information between the past and the future is infinite. It is assumed that the number of observable states is finite and the number of hidden states is countably infinite. Under this assumption, we show that the block mutual information of a hidden Markov process is upper bounded by a power law determined by the tail index of the hidden state distribution. Moreover, we exhibit three examples of processes. The first example, considered previously, is nonergodic and the mutual information between the blocks is bounded by the logarithm of the block length. The second example is also nonergodic but the mutual information between the blocks obeys a power law. The third example obeys the power law and is ergodic.     

Microwave-assisted Cannizzaro reaction—Optimisation of reaction conditions

The microwave-assisted Cannizzaro reaction was studied in order to develop fully reproducible synthetic protocols for transformation of aldehydes to carboxylic acid and alcohols. Optimised were the following process parameters: power, temperature, and time. Aromatic, heteroaromatic and aliphatic aldehydes were used in the studies. It was found that furfural, thiophene-2-carbaldehyde, pyridinecarboxaldehyde and aromatic aldehydes react under mild conditions, while 1-methyl-pyrrole-2-carboxaldehyde derivatives and aliphatic aldehydes require more drastic reaction conditions and a longer exposure time to microwave radiation.     

Low-Temperature TLC-MS of Essential Oils from Five Different Sage (Salvia) Species

JPC – Journal of Planar Chromatography – Modern TLC - In a previous paper we discussed the possibility of fractionating the essential oils of different sage species by low-temperature...