Contact properties of surfaces in r-3 with corank 1 singularities

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Through ring umbrella inversion of a molecular rattle

We report theoretical investigations on some [Ring]Li--(+) compounds, which can exhibit a through ring umbrella like inversion. Our studies predict cyclononatetraenyllithium to be molecular rattle, in which such inversions can occur. The potential energy for the motion is a double well, with an activation barrier of 11.50 kcal/mol. We find that the lithium should go through the ring easily by an excitation to nu = 17 vibrational level. (C) 2002 Elsevier Science B.V. All rights reserved.

Free energy surface reconstruction from umbrella samples using Gaussian process regression

We demonstrate how the Gaussian process regression approach can be used to efficiently reconstruct free energy surfaces from umbrella sampling simulations. By making a prior assumption of smoothness and taking account of the sampling noise in a consistent fashion, we achieve a significant improvement in accuracy over the state of the art in two or more dimensions or, equivalently, a significant cost reduction to obtain the free energy surface within a prescribed tolerance in both regimes of spatially sparse data and short sampling trajectories. Stemming from its Bayesian interpretation the method provides meaningful error bars without significant additional computation. A software implementation is made available on www.libatoms.org.

Free energy surface reconstruction from umbrella samples using Gaussian process regression II: Multiple collective variables

We demonstrate how a prior assumption of smoothness can be used to enhance the reconstruction of free energy profiles from multiple umbrella sampling simulations using the Bayesian Gaussian process regression approach. The method we derive allows the concurrent use of histograms and free energy gradients and can easily be extended to include further data. In Part I we review the necessary theory and test the method for one collective variable. We demonstrate improved performance with respect to the weighted histogram analysis method and obtain meaningful error bars without any significant additional computation. In Part II we consider the case of multiple collective variables and compare to a reconstruction using least squares fitting of radial basis functions. We find substantial improvements in the regimes of spatially sparse data or short sampling trajectories. A software implementation is made available on www.libatoms.org.

Whitney's type theorems for infinite dimensional spaces

It is proved that for any $f$ is an element of $C^k(L,R)$, where k is a natural number and L is a closed linear subspace of a nuclear Frechet space $X$, the function $f$ can be extended to a function of class $C^{k-1}$ defined on the entire space $X$. It is also proved that for any $f$ is an element of $C^k(L, R)$, where $k$ is a natural number of infinity and L is a closed linear subspace of a dual $X$ of a nuclear Frechet space, the function $f$ can be extended to a function of class $C^k$ defined on the entire space $X$. In addition, it is proved that under these conditions, the existence of a linear extension operator is equivalent to the complementability of the subspace.

A white umbrella in México

UANL

Treatment of nonlinear optical properties due to large amplitude anharmonic vibrational motions: umbrella motion in NH3

A general reduced dimensionality finite field nuclear relaxation method for calculating vibrational nonlinear optical properties of molecules with large contributions due to anharmonic motions is introduced. In an initial application to the umbrella (inversion) motion of NH3 it is found that difficulties associated with a conventional single well treatment are overcome and that the particular definition of the inversion coordinate is not important. Future applications are described