Theoretical investigation of excited states of molecules. An application on the nitrogen molecule

Diverse existing lines for the calculation of excited states are exposed, with an emphasis on those methods that consider both types of correlation energy: the dynamic and the non-dynamic one. We analyze the possibility of to calculate the dynamic correlation energy using a correlation energy density functional applied to a multi-determinantal wavefunction, which would include the non-dynamic correlation energy, versus the use of mono-determinantal wavefunctions, which are not able to include the long-range correlation energy, and versus the use of variational or perturbative calculations from multi-determinantal wavefunctions, with their excessive computational cost. The results obtained with several methods are compared. Contribution to the Serafin Fraga Memorial Issue.     

Vicinal fluorine-fluorine coupling constants: Fourier analysis

Stereochemical dependences of vicinal fluorine-fluorine nuclear magnetic resonance coupling constants (3JFF) have been studied with the multiconfigurational self-consistent field in the restricted active space approach, with the second-order polarization propagator approximation (SOPPA), and with density functional theory. The SOPPA results show the best overall agreement with experimental couplings. The relationship with the dihedral angle between the coupled fluorines has been studied by Fourier analysis, the result is very different from that of proton-proton couplings. The Fourier coefficients do not resemble those of a typical Karplus equation. The four nonrelativistic contributions to the coupling constants of 1,2-difluoroethane configurations have been studied separately showing that up to six Fourier coefficients are required to reproduce the calculated values satisfactorily. Comparison with Fourier coefficients for matching hydrogen fluoride dimer configurations suggests that the higher order Fourier coefficients (Cn> or =3) originate mainly from through-space Fermi contact interaction. The through-space interaction is the main reason 3JFF do not follow the Karplus equation.     

Maximal Elements Under Reference-Dependent Preferences with Applications to Behavioral Traps and Games

We study reference-dependent preference relations defined by a real-valued bivariate function and prove an existence criterion for maximal elements. Then we formulate a generalized version of the well-known Brondsted maximum principle and apply it to behavioral traps and Nash equilibrium in games with preference relations that are not necessarily partial orders.     

Assessment of DFT functionals with fluorine–fluorine coupling constants†

Density functional theory (DFT) calculations of nuclear magnetic resonance (NMR) spin–spin coupling constants (SSCCs) provide an important contribution for understanding experimentally observed values. It is known that calculated SSCCs using DFT methods correlate well with those experimentally measured. Unlike most of SSCCs, in fluorine compounds, fluorine–fluorine SSCC J_FF shows that the Fermi contact (FC) term is not dominant, particularly for J_FF in polyfluorinated organic molecules. In order to devise a DFT approach that would correctly reproduce the variation of SSCCs within a series of fluorine compounds, we test several DFT-based approaches, using different exchange and correlation functionals. Isotropic contributions to NMR fluorine–fluorine coupling constants (FC, spin-dipolar, SD, paramagnetic spin-orbit, PSO, and diamagnetic spin-orbit, DSO) have been calculated. Results show that DFT methods give appropriate values for ⁿJ_FF (n = 4 to 7), while for geminal and vicinal J_FF present large deviations from experimental values. For the latter SSCCs (²J_FF and ³J_FF), the four contributions (FC, SD, PSO and DSO) are analysed as a function of the local and nonlocal exchange in 1,1- and 1,2-difluoroethylene. Although FC term is not dominant for these SSCCs, the variation of this contribution with exchange is remarkable. On the other hand, SD and PSO contributions can be suitably computed without and with exact exchange, respectively.     

Localized turbulent flows on scouring granular beds

In many applications a sustained, localized turbulent flow scours a cohesionless granular bed to form a pothole. Here we use similarity methods to derive a theoretical formula for the equilibrium depth of the pothole. Whereas the empirical formulas customarily used in applications contain numerous free exponents, the theoretical formula contains a single one, which we show can be determined via the phenomenological theory of turbulence. Our derivation affords insight into how a state of dynamic equilibrium is attained between a granular bed and a localized turbulent flow.     

Semistrictly quasiconvex mappings and non-convex vector optimization

This paper introduces a new class of non-convex vector functions strictly larger than that of P-quasiconvexity, with P ^m being the underlying ordering cone, called semistrictly ( ^m\ –int P)-quasiconvex functions. This notion allows us to unify various results on existence of weakly efficient (weakly Pareto) optima. By imposing a coercivity condition we establish also the compactness of the set of weakly Pareto solutions. In addition, we provide various characterizations for the non-emptiness, convexity and compactness of the solution set for a subclass of quasiconvex vector optimization problems on the real-line. Finally, it is also introduced the notion of explicit ( ^m\ –int P)-quasiconvexity (equivalently explicit (int P)-quasiconvexity) which plays the role of explicit quasiconvexity (quasiconvexity and semistrict quasiconvexity) of real-valued functions.Acknowldegements.The author wishes to thank both referees for their careful reading of the paper, their comments, remarks, helped to improve the presentation of some results. One of the referee provided the references [5, 6] and indirectly [20].     

Vector Equilibrium Problems Under Asymptotic Analysis

Given a closed convex set K in Rⁿ; a vector function F:K×K R^m; a closed convex (not necessarily pointed) cone P(x) in ^m with non-empty interior, PP(x) Ø, various existence results to the problemfind xK such that F(x,y)- int P(x) y K under P(x)-convexity/lower semicontinuity of F(x,) and pseudomonotonicity on F, are established. Moreover, under a stronger pseudomonotonicity assumption on F (which reduces to the previous one in case m=1), some characterizations of the non-emptiness of the solution set are given. Also, several alternative necessary and/or sufficient conditions for the solution set to be non-empty and compact are presented. However, the solution set fails to be convex in general. A sufficient condition to the solution set to be a singleton is also stated. The classical case P(x)=^m ₊ is specially discussed by assuming semi-strict quasiconvexity. The results are then applied to vector variational inequalities and minimization problems. Our approach is based upon the computing of certain cones containing particular recession directions of K and F.