Computational spectroscopy of helium-solvated molecules: effective inertia, from small He clusters toward the nanodroplet regime

Accurate computer simulations of the rotational dynamics of linear molecules solvated in He clusters indicate that the large-size (nanodroplet) regime is attained quickly for light rotors (HCN) and slowly for heavy ones (OCS, N2O, and CO2), thus challenging previously reported results. Those results spurred the view that the different behavior of light rotors with respect to heavy ones-including a smaller reduction of inertia upon solvation of the former-would result from the lack of adiabatic following of the He density upon molecular rotation. We have performed computer experiments in which the rotational dynamics of OCS and HCN molecules was simulated using a fictitious inertia appropriate to the other molecule. These experiments indicate that the approach to the nanodroplet regime, as well as the reduction of the molecular inertia upon solvation, is determined by the anistropy of the potential, more than by the molecular weight. Our findings are in agreement with recent infrared and/or microwave experimental data which, however, are not yet totally conclusive by themselves.     

Rotational dynamics of CO solvated in small He clusters: a quantum Monte Carlo study

The rotational dynamics of CO single molecules solvated in small He clusters (CO @ HeN) has been studied using reptation quantum Monte Carlo simulations for cluster sizes up to N = 30. Our results are in good agreement with the rotovibrational features of the infrared spectrum recently determined for this system and provide a deep insight into the relation between the structure of the cluster and its dynamics. Simulations for large N also provide a prediction of the effective moment of inertia of CO in the He nanodroplet regime, which has not been measured so far.     

Interaction of l-malic acid with alkaline metals and open chain polyammonium cations in aqueous solution

This work reports a potentiometric, calorimetric and spectropolarimetric ultraviolet circular dichroism (UV/CD) study of the interaction of l-malic acid with alkaline metals or (poly)ammonium (methylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, spermine, tetraethylenepentamine and pentaethylenehexamine) cations. Stability data (logK, DeltaG(0)) were obtained potentiometrically for the l-malic acid with (poly)ammonium cations systems; calorimetric measurements (25 degrees C) made it possible to obtain DeltaH(0) and TDeltaS(0) values for the complexes formed in the systems under examination. logK values calculated (for the reaction: H(i)A(i+)+H(j)L((j-z))=ALH(r)((i+j-z)), with r=i+j) range between 0.8 and 4.6, i.e., the interactions are from weak to fairly strong while maximum stability for each system is given by the species with the highest z(anion)xz(cation) (z=charge) value. Enthalpy changes associated with reactions H(n)A(n+)+L(2-)=ALH(n)((n-2)) and H(n)A(n+)+HL(-)=ALH(n+1)((n-1)) are always positive and increase progressively with n. The same is valid for T DeltaS(0) values, which indicate that these species are entropically stabilized, as expected for electrostatic interactions. It was verified that the UV/CD signal depends on both ionic medium and ionic strength value; for comparison, we used the l-malic acid signal recorded in tetramethylammonium chloride as baseline background salt (as in potentiometry). UV/CD spectra were recorded for solutions containing both cationic and anionic species. When the cation was a protonated polyamine, CD spectra calculations were performed for most stable ion pairs: the results show remarkable differences in Deltaepsilon (dm(3) mol(-1) cm(-1)) values at 205 nm (which is the l-malate UV/CD lambda(max)) between the chiral ligand and its complex with a polyamine.     

Mixed proton complexes of aminoacids and carboxylic ligands in aqueous solution

Formation and stability of proton-mixed ligand complexes have been studied for the systems H(+)-lysine-aspartic acid, H(+)-lysine-succinic acid and H(+)-glycine malonic acid, in aqueous solution at 25 degrees , by potentiometric technique using the (H(+))-glass electrode. For all these systems it has been found that the species ABH(j) (A and B, first and second ligand, respectively; j = 1, 2, ... m + n - 1; m and n are the maximum protonation degrees of the two ligands, respectively) are formed. The stability of these species is discussed with respect to various factors and, in particular, as a function of speciation problems.     

Synthesis, structural determination and photo-antiproliferative activity of new 3-pyrazolyl or -isoxazolyl substituted 4-hydroxy-2(1H)-quinolinones

A convenient route to new 3-quinolinonyl-pyrazoles and isoxazoles is described through cyclization of 3-[(E)-3-(dimethylamino)-2-propenoyl]-4-hydroxy-1-methyl-2(1H)-quinolinone. The phototoxicity as well as the cytotoxic activities of the title compounds are evaluated against leukemia- and adenocarcinoma-derived cell lines in comparison to the normal human keratinocytes.     

Derivative-free methods for mixed-integer nonsmooth constrained optimization

Computational Optimization and Applications - In this paper, mixed-integer nonsmooth constrained optimization problems are considered, where objective/constraint functions are available only as the...     

Classical limit of the quantized hyperbolic toral automorphisms

The canonical quantization of any hyperbolic symplectomorphismA of the 2-torus yields a periodic unitary operator on aN-dimenional Hilbert space,N=1/h. We prove that this quantum system becomes ergodic and mixing at the classical limit (N,N prime) which can be interchanged with the time-average limit. The recovery of the stochastic behaviour out of a periodic one is based on the same mechanism under which the uniform distribution of the classical periodic orbits reproduces the Lebesgue measure: the Wigner functions of the eigenstates, supported on the classical periodic orbits, are indeed proved to become uniformly speread in phase space.     

A Construction of the Level 3 Modules for the Affine Lie Algebra and a New Combinatorial Identity of the Rogers-Ramanujan Type

We obtain a vertex operator construction of level 3 standard representations for the affine Lie algebra . As a corollary, we also get new conbinatorial identities.

     

On the extreme spectral properties of Toeplitz matrices generated byL 1 functions with several minima/maxima

In this paper we are concerned with the asymptotic behavior of the smallest eigenvalue ₁ ⁽ⁿ⁾ of symmetric (Hermitian)n ×n Toeplitz matricesT _n (f) generated by an integrable functionf defined in [–, ]. In [7, 8, 11] it is shown that ₁ ⁽ⁿ⁾ tends to essinff =m _f in the following way: ₁ ⁽ⁿ⁾ –m _f 1/n ^2k . These authors use three assumptions:A1)f –m _f has a zero inx =x ₀ of order 2k.A2)f is continuous and at leastC ^2k in a neighborhood ofx ₀.A3)x =x ₀ is the unique global minimum off in [–, ]. In [10] we have proved that the hypothesis of smoothnessA2 is not necessary and that the same result holds under the weaker assumption thatf L ¹[–, ]. In this paper we further extend this theory to the case of a functionf L ¹[–, ] having several global minima by suppressing the hypothesisA3 and by showing that the maximal order 2k of the zeros off –m _f is the only parameter which characterizes the rate of convergence of ₁ ⁽ⁿ⁾ tom _f .     

Minimum blocking configurations

Some results on configurations realizing minimum blocking sets of a finite projective plane are obtained by introducing a suitable attraction property.Dedicated to Professor M. Scafati Tallini on the occasion of her 65th birthday