New form of polymeric nitrogen from dynamic shock simulation.

For many years there has been significant interest in polymeric phases of nitrogen at low pressure for potential application as an energetic material. This was the result of years of theoretical work indicating potentially meta-stable polymeric nitrogen. Experimental evidence of both an amorphous phase and a cubic-gauche phase has added greatly to this interest [A. F. Goncharov, E. A. Gregoryanz, H. K. Mao, Z. Liu, and R. J. Hemley, Phys. Rev. Lett. 85, 1262 (2000); M. I. Eremets, R. J. Hemley, H. K. Mao, and E. Gregoryanz, Nature (London) 411, 170 (2001)]. While most of the theoretical work has been done on the many crystal phases of nitrogen, little work has been done on simulating amorphous polymeric nitrogen. The original goal of this work was to simulate amorphous polymeric nitrogen at low pressure; however, we unexpectedly found a new form of polymeric nitrogen. Starting from first principles dynamic shock simulation of cubic-gauche nitrogen [W. D. Mattson and R. Balu, Phys. Rev. B 83, 174105 (2011)] we demonstrate a new low pressure porous form that exhibits stability at low temperatures. We describe the detailed procedure of obtaining this structure as well as some of its physical characteristics. Finally, we explore composite structures of this new form of polymeric nitrogen and their possible relationship to an amorphous form.

Molecular hydrogen adsorbed on benzene: Insights from a quantum Monte Carlo study.

We present a quantum Monte Carlo study of the hydrogen-benzene system where binding is very weak. We demonstrate that the binding is well described at both variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) levels by a Jastrow correlated single determinant geminal wave function with an optimized compact basis set that includes diffuse orbitals. Agreement between VMC and fixed-node DMC binding energies is found to be within 0.18 mhartree, suggesting that the calculations are well converged with respect to the basis. Essentially the same binding is also found in independent DMC calculations using a different trial wave function of a more conventional Slater-Jastrow form, supporting our conclusion that the binding energy is accurate and includes all effects of correlation. We compare with previous calculations, and we discuss the physical mechanisms of the interaction, the role of diffuse basis functions, and the charge redistribution in the bond.

High strength films from oriented, hydrogen-bonded "graphamid" 2D polymer molecular ensembles.

The linear polymer poly(p-phenylene terephthalamide), better known by its tradename Kevlar, is an icon of modern materials science due to its remarkable strength, stiffness, and environmental resistance. Here, we propose a new two-dimensional (2D) polymer, "graphamid", that closely resembles Kevlar in chemical structure, but is mechanically advantaged by virtue of its 2D structure. Using atomistic calculations, we show that graphamid comprises covalently-bonded sheets bridged by a high population of strong intermolecular hydrogen bonds. Molecular and micromechanical calculations predict that these strong intermolecular interactions allow stiff, high strength (6-8 GPa), and tough films from ensembles of finite graphamid molecules. In contrast, traditional 2D materials like graphene have weak intermolecular interactions, leading to ensembles of low strength (0.1-0.5 GPa) and brittle fracture behavior. These results suggest that hydrogen-bonded 2D polymers like graphamid would be transformative in enabling scalable, lightweight, high performance polymer films of unprecedented mechanical performance.

QMCPACK: an open source ab initio quantum Monte Carlo package for the electronic structure of atoms, molecules and solids.

QMCPACK is an open source quantum Monte Carlo package for ab initio electronic structure calculations. It supports calculations of metallic and insulating solids, molecules, atoms, and some model Hamiltonians. Implemented real space quantum Monte Carlo algorithms include variational, diffusion, and reptation Monte Carlo. QMCPACK uses Slater-Jastrow type trial wavefunctions in conjunction with a sophisticated optimizer capable of optimizing tens of thousands of parameters. The orbital space auxiliary-field quantum Monte Carlo method is also implemented, enabling cross validation between different highly accurate methods. The code is specifically optimized for calculations with large numbers of electrons on the latest high performance computing architectures, including multicore central processing unit and graphical processing unit systems. We detail the program's capabilities, outline its structure, and give examples of its use in current research calculations. The package is available at http://qmcpack.org.