Improved diffusion Monte Carlo propagators for bosonic systems using Itô calculus

The construction of importance sampled diffusion Monte Carlo (DMC) schemes accurate to second order in the time step is discussed. A central aspect in obtaining efficient second order schemes is the numerical solution of the stochastic differential equation (SDE) associated with the Fokker-Plank equation responsible for the importance sampling procedure. In this work, stochastic predictor-corrector schemes solving the SDE and consistent with It? calculus are used in DMC simulations of helium clusters. These schemes are numerically compared with alternative algorithms obtained by splitting the Fokker-Plank operator, an approach that we analyze using the analytical tools provided by Ito; calculus. The numerical results show that predictor-corrector methods are indeed accurate to second order in the time step and that they present a smaller time step bias and a better efficiency than second order split-operator derived schemes when computing ensemble averages for bosonic systems. The possible extension of the predictor-corrector methods to higher orders is also discussed.     

Predictive/fitting capabilities of differential constitutive models for polymer melts—reduction of nonlinear parameters in the eXtended Pom-Pom model

A phenomenological modification of the eXtended Pom-Pom (XPP) model is proposed with the aim to reduce the number of free nonlinear parameters. The modified XPP model includes three parameters per mode in total (two linear viscoelastic parameters—linear relaxation time λ and shear modulus G, and one nonlinear parameter). The original XPP model contains five parameters (two linear viscoelastic parameters and three nonlinear ones, one nonlinear parameter participates in the second normal stress difference prediction). The predictive/fitting capabilities of the modified model are compared with the Giesekus, eXtended Pom-Pom, and modified Leonov models using various low-density PE materials in steady and transient shear and uniaxial elongational flows. It has been found that the modified model is capable of predicting/fitting the rheological properties, with the exception of the second normal stress difference, for studied LDPE materials with sufficient accuracy, including strain hardening in uniaxial elongational flow.     

DFT characterization of the reaction pathways for terminal- to μ-hydride isomerisation in synthetic models of the [FeFe]-hydrogenase active site

The mechanism of terminal- to μ-hydride isomerisation in models of synthetic complexes resembling the [FeFe]-hydrogenase active site has been elucidated by DFT calculations, revealing that Ray-Dutt reaction pathways are generally favoured, and providing some clues for the rational design of novel synthetic catalysts to produce H(2).