Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH₃, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH₃ so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution.     

Diboron Bonds Between BX3 (X=H,F, CH3) and BYZ2 (Y=H,F; Z=CO,N2, CNH)

The ability of B atoms on two different molecules to engage with one another in a noncovalent diboron bond is studied by ab initio calculations. Due to electron donation from its substituents, the trivalent B atom of BYZ₂ (Z=CO, N₂, and CNH; Y=H and F) has the ability to in turn donate charge to the B of a BX₃ molecule (X=H, F, and CH₃), thus forming a B⋅⋅⋅B diboron bond. These bonds are of two different strengths and character. BH(CO)₂ and BH(CNH)₂, and their fluorosubstituted analogues BF(CO)₂ and BF(CNH)₂, engage in a typical noncovalent bond with B(CH₃)₃ and BF₃, with interaction energies in the 3–8 kcal/mol range. Certain other combinations result in a much stronger diboron bond, in the 26–44 kcal/mol range, and with a high degree of covalent character. Bonds of this type occur when BH₃ is added to BH(CO)₂, BH(CNH)₂, BH(N₂)₂, and BF(CO)₂, or in the complexes of BH(N₂)₂ with B(CH₃)₃ and BF₃. The weaker noncovalent bonds are held together by roughly equal electrostatic and dispersion components, complemented by smaller polarization energy, while polarization is primarily responsible for the stronger ones.     

Comparison of Bifurcated Halogen with Hydrogen Bonds

Bifurcated halogen bonds are constructed with FBr and FI as Lewis acids, paired with NH₃ and NCH bases. The first type considered places two bases together with a single acid, while the reverse case of two acids sharing a single base constitutes the second type. These bifurcated systems are compared with the analogous H-bonds wherein FH serves as the acid. In most cases, a bifurcated system is energetically inferior to a single linear bond. There is a larger energetic cost to forcing the single σ-hole of an acid to interact with a pair of bases, than the other way around where two acids engage with the lone pair of a single base. In comparison to FBr and FI, the H-bonding FH acid is better able to participate in a bifurcated sharing with two bases. This behavior is traced to the properties of the monomers, in particular the specific shape of the molecular electrostatic potential, the anisotropy of the orbitals of the acid and base that interact directly with one another, and the angular extent of the total electron density of the two molecules.     

Use of ETAAS,FAAS and ICP-OES for production and post-certification monitoring of a multielemental certified reference material according to national regulation limits for elements in drinking water

Accreditation and Quality Assurance - This paper describes the development of a certified reference material (CRM), produced in the National Institute of Quality from Peru (INACAL) in order to...     

Intertwining the geodesic flow and the Schr?dinger group on hyperbolic surfaces

We construct an explicit intertwining operator L{\mathcal L} between the Schr?dinger group e^{it \frac\triangle2}{e^{it \frac\triangle2}} and the geodesic flow on certain Hilbert spaces of symbols on the cotangent bundle T*X _Γ of a compact hyperbolic surface X _Γ = Γ\D. We also define Γ-invariant eigendistributions of the geodesic flow PS_{j, k, nj,-nk}{PS_{j, k, \nu_j,-\nu_k}} (Patterson-Sullivan distributions) out of pairs of \triangle{\triangle} -eigenfunctions, generalizing the diagonal case j = k treated in Anantharaman and Zelditch (Ann. Henri Poincaré 8(2):361–426, 2007). The operator L{\mathcal L} maps PS_{j, k, nj,-nk}{PS_{j, k, \nu_j,-\nu_k}} to the Wigner distribution W^G_j,k{W^{\Gamma}_{j,k}} studied in quantum chaos. We define Hilbert spaces H_PS{\mathcal H_{PS}} (whose dual is spanned by {PS_{j, k, nj,-nk}{PS_{j, k, \nu_j,-\nu_k}}}), resp. H_W{\mathcal H_W} (whose dual is spanned by {W^G_j,k}{\{W^{\Gamma}_{j,k}\}}), and show that L{\mathcal L} is a unitary isomorphism from H_W ? H_PS.{\mathcal H_{W} \to \mathcal H_{PS}.}     

Equilibria of two-sided matching games with common preferences

Problems of matching have long been studied in the operations research literature (assignment problem, secretary problem, stable marriage problem). All of these consider a centralized mechanism whereby a single decision maker chooses a complete matching which optimizes some criterion. This paper analyzes a more realistic scenario in which members of the two groups (buyers–sellers, employers–workers, males–females) randomly meet each other in pairs (interviews, dates) over time and form couples if there is mutual agreement to do so. We assume members of each group have common preferences over members of the other group. Generalizing an earlier model of Alpern and Reyniers [Alpern, S., Reyniers, D.J., 2005. Strategic mating with common preferences. J. Theor. Biol. 237, 337–354], we assume that one group (called males) is r   times larger than the other, r?1$r?1$. Thus all females, but only 1/r$1/r$ of the males, end up matched. Unmatched males have negative utility -c$-c$. We analyze equilibria of this matching game, depending on the parameters r   and c$c$. In a region of (r,c)$(r\text{,}c)$ space with multiple equilibria, we compare these, and analyze their ‘efficiency’ in several respects. This analysis should prove useful for designers of matching mechanisms who have some control over the sex ratio (e.g. by capping numbers of males at a ‘singles event’or by having ‘ladies free’ nights) or the nonmating cost c (e.g. tax benefits to married couples).     

Computing inertia sets using atoms

We consider the problem of computing inertia sets for graphs. By using tools for combining the inertia sets of smaller graphs we can reduce this problem to understanding the inertia sets for three-connected graphs that are not joins. We term such graphs atoms and give the inertia sets for all atoms on at most seven vertices. This can be used to compute the inertia sets for all graphs on at most seven vertices.