Efficient sampling of atomic configurational spaces.

We describe a method to explore the configurational phase space of chemical systems. It is based on the nested sampling algorithm recently proposed by Skilling (AIP Conf. Proc. 2004, 395; J. Bayesian Anal. 2006, 1, 833) and allows us to explore the entire potential energy surface (PES) efficiently in an unbiased way. The algorithm has two parameters which directly control the trade-off between the resolution with which the space is explored and the computational cost. We demonstrate the use of nested sampling on Lennard-Jones (LJ) clusters. Nested sampling provides a straightforward approximation for the partition function; thus, evaluating expectation values of arbitrary smooth operators at arbitrary temperatures becomes a simple postprocessing step. Access to absolute free energies allows us to determine the temperature-density phase diagram for LJ cluster stability. Even for relatively small clusters, the efficiency gain over parallel tempering in calculating the heat capacity is an order of magnitude or more. Furthermore, by analyzing the topology of the resulting samples, we are able to visualize the PES in a new and illuminating way. We identify a discretely valued order parameter with basins and suprabasins of the PES, allowing a straightforward and unambiguous definition of macroscopic states of an atomistic system and the evaluation of the associated free energies.

Image deconvolution using a Gaussian scale mixtures model to approximate the wavelet sparseness constraint

This paper proposes to use an extended Gaussian Scale Mixtures (GSM) model instead of the conventional ℓ1 norm to approximate the sparseness constraint in the wavelet domain. We combine this new constraint with subband-dependent minimization to formulate an iterative algorithm on two shift-invariant wavelet transforms, the Shannon wavelet transform and dual-tree complex wavelet transform (DTCWT). This extented GSM model introduces spatially varying information into the deconvolution process and thus enables the algorithm to achieve better results with fewer iterations in our experiments. ©2009 IEEE.