Research Program from BAA - Chemical Sciences

7.0 Overview

The ARO Chemical Sciences Division supports research efforts to advance the Army and Nation's knowledge and understanding of the fundamental properties and processes governing molecules and their interactions in materials and chemical systems. The Division encourages proposals that promote basic research to develop methods for accurately predicting the pathways, intermediates, and energy transfer of specific reactions, to understand the fundamental processes governing electrochemical reactions and transport of species, and to discover the relationships between macromolecular microstructure, architecture, functionality, and macroscopic properties. In addition, these efforts will likely lead to new methods for synthesizing and analyzing molecules and materials that will open the door to future studies not feasible with current approaches.

7.1 Molecular Structure and Dynamics

The goal of this Program is to determine the pathways and intermediates for fast reactions of molecules in gas and condensed phases at high temperatures and pressures, and to develop theories that are capable of accurately describing and predicting these phenomena. In the long term, these studies may serve as the basis for the design of future propellants, explosives, and sensors. This Program is divided into two research thrusts: (i) Reaction Dynamics and (ii) Computational Modeling.

Research in the Reaction Dynamics thrust explores energy transfer mechanisms in molecular systems. In particular, research is focused on understanding dynamic processes such as roaming radicals, chemical reactions in solid state crystals and heterogeneous mixtures, phase transformations at extreme conditions, and control of processes using both shaped laser pulses and continuous wave laser beams. Studies that yield new insights on the decomposition pathways of energetic molecules, both in the gas and condensed phases, are also of interest.

Research in the Computational Modeling thrust is focused on the development and validation of theories for describing and predicting the properties of chemical reactions and molecular phenomena in gas and condensed phases. In particular, research targeted at the development and implementation of novel theoretical computational chemistry methods is of interest. Ideally, such methods will go beyond current theories to allow for efficient, accurate, and a priori prediction of thermochemical properties. Such methods may take advantage of near-ideal parallel processing on massive computer clusters, or they may seek to solve current scaling problems through novel implementation of unprecedented computer algorithms. The accurate prediction of intermolecular forces for problems in solid-state chemistry, such as the prediction of x-ray crystal structures, is also of current interest.

Technical Point of Contact: Dr. James Parker, e-mail:james.k.parker30.civ@mail.mil, (919) 549-4293

7.2 Electrochemistry

This Program supports fundamental electrochemical studies to understand and control the physics and chemistry that govern electrochemical redox reactions and transport of species, and how these are coupled with electrode, catalysis, electrolyte, and interface. Research includes ionic conduction in electrolytes, electrocatalysis, interfacial electron transfer, transport through coatings, surface films and polymer electrolytes, activation of carbon-hydrogen and carbon-carbon bonds, and spectroscopic techniques to selectively probe electrode electrolyte interfaces. Novel electrochemical synthesis, investigations into the effect of microenvironment on chemical reactivity, and quantitative models of electrochemical systems are also encouraged.

This Program is divided into two research thrusts, although other areas of electrochemical research may be considered: (i) Reduction-oxidation (Redox) Chemistry and Electrocatalysis, and (ii) Transport of Electroactive Species. The Redox Chemistry and Electrocatalysis thrust supports research to understand how material and morphology affect electron transfer and electrocatalysis, tailor electrodes and electrocatalysts at a molecular level, and discover new spectroscopic and electrochemical techniques for probing surfaces and selected species on those surfaces. The Transport of Electroactive Species thrust identifies and supports research to uncover the mechanisms of transport through heterogeneous, charged environments such as polymers and electrolytes, to design tailorable electrolytes based on new polymers and ionic liquids, and to explore new methodologies and computational approaches to study the selective transport of species in charged environments.

Technical Point of Contact: Robert Mantz, e-mail: robert.a.mantz.civ@mail.mil, (919) 549-4309

7.3 Polymer Chemistry

The goal of this Program is to understand the molecular-level link between polymer microstructure, architecture, functionality, and macroscopic properties. Research in this Program may ultimately enable the design and synthesis of functional polymeric materials that give the Soldier new and improved protective and sensing capabilities as well as capabilities not yet imagined. This Program is divided into two research thrusts: (i) Precision Polymeric Materials and (ii) Responsive Polymeric Materials. Within these thrusts, high-risk, high-payoff research is identified and supported to pursue the Program's long-term goal. Additionally, research efforts that connect innovative polymer chemistry with the comprehensive characterization of polymeric materials are of joint interest with the Mechanical Behavior of Materials Program in the ARO Materials Science Division.

The Precision Polymeric Materials thrust supports research aimed at developing new approaches for synthesizing polymers with precisely-defined molecular weight, microstructure (monomer sequence and tacticity), branching, and functional group location, and on using self assembly to create precise, complex polymer structure with diverse functions and new properties. Areas of interest include: new polymerization methodologies, the design and synthesis of new monomers with controlled reactivity, the design and synthesis of new catalysts that give precision control over polymer microstructure, and self-assembly of polymers into functional hierarchical nanostructures. The Responsive Polymeric Materials thrust focuses on the design and synthesis of novel polymers that undergo predictable conformational and/or chemical changes in response to specific external stimuli. Of particular interest are research efforts in the areas of polymer mechanochemistry, self-immolative polymers, and reconfigurable materials.

Technical Points of Contact: Dr. Dawanne Poree (contractor), e-mail: dawanne.e.poree.ctr@mail.mil, (919) 549-4238; Robert Mantz (Acting), e-mail: robert.a.mantz.civ@mail.mil, (919) 549-4309

7.4 Reactive Chemical Systems

This Program supports basic research with Army relevance in surfaces, catalysis, and organized assemblies. The goals of the Program are to explore reactive chemical systems and related processes such as adsorption, desorption, and the catalytic processes occurring at surfaces and interfaces, and the structure and function of supramolecular assemblies. Through the study of these processes and structures, the Program seeks to develop a molecular level understanding of catalytic reactions, functionalized surfaces, and organized assemblies that may lead to future materials for protection and sensing. The Surfaces and Catalysis thrust supports research on understanding the kinetics and mechanisms of reactions occurring at surfaces and interfaces and the development of new methods to investigate the interactions of small organic molecules and biological molecules on surfaces. Development of reactive multifunctional materials is also included in this Program. A particular area of interest is the interface between nanostructures and biomolecules, including biocolloids, to generate advanced materials. The Organized Assemblies thrust supports research aimed at exploring the properties and capabilities of self-assembled and supramolecular structures, including their functionality, and how to control assembly in different environments. A specific area of interest is the design and understanding of stimuli-responsive materials.

In addition, the emerging field of dynamic, responsive, multi-functional materials has great potential to provide revolutionary new capabilities. A specific technical area in this field is "targeting and triggering" in which a specific chemical (or event) is targeted (recognized) and that recognition triggers a response. Particular technical challenges of interest include selective and reversible recognition, amplification, and multi-responsive systems. Alternative approaches to selective, yet reversible, recognition are needed. Amplification includes an understanding of how to amplify the response from a single molecular recognition event to a multi-molecular response with approaches that promote chain reactions, self-amplification or cascade-type reactions within a single system. Multi-responsive systems in which specific stimuli trigger distinct responses are also of interest.

Technical Point of Contact: Dr. Jennifer Becker, e-mail:jennifer.j.becker.civ@mail.mil, (919) 549-4224

 

Last Update / Reviewed: July 31, 2012