2013 Heavy Element Chemistry and Separations Science Principal Investigators’ Meeting Gaithersburg, MD April 21–24, 2013 Office of Basic Energy Sciences (BES) Chemical Sciences, Geosciences, and Biosciences Division Program and Abstracts for the 2013 Heavy Element Chemistry and Separations Science Principal Investigators’ Meeting Gaithersburg Marriott Washingtonian Center Gaithersburg, MD April 21–24, 2013 Chemical Sciences, Geosciences, and Biosciences Division Office of Basic Energy Sciences Office of Science U.S. Department of Energy Cover art created with Wordle, a toy for generating “word clouds” from text using the Goudy Bookletter 1911 font. The text bodies from the abstracts contained in the following program were the basis of the word cloud. The research grants and contracts described in this document are, with the exception of the invited speakers, supported by the U.S. DOE Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. DISCLAIMER This report is a compilation of accounts of work sponsored by an agency of the United States Government. Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. ii Foreword This abstract booklet provides a record of the twelfth U.S. Department of Energy contractors’ meeting in separations sciences and the seventh in heavy element chemistry. This year the meeting is co-chaired by Dr. David Shuh (Lawrence Berkeley National Laboratory) and Professor Aurora Clark (Washington State University). The Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences and its predecessors have sponsored research in heavy element chemistry and separations sciences for over sixty years. Although these are distinct disciplines, they have much in common for many reasons, in particular because novel separations research is needed to produce pure heavy- element samples and because heavy element chemistry provides the basis for many separations processes. This is the sixth joint meeting of these programs. The objective of this meeting is to provide a fruitful environment in which researchers with common interests will present and exchange information about their activities, will build collaborations among research groups with mutually reinforcing strengths, will identify needs of the research community, and will focus on opportunities for future research directions. The agenda includes invited talks, oral presentations, and poster presentations, organized so that papers in related disciplines are loosely clustered together. With ample time for discussion and interactions, we emphasize that this is an informal meeting for exchange of information and building of collaborations; it is not a review of researchers’ achievements or a forum to choose future directions. We appreciate the privilege of serving as the managers of our respective research programs. In carrying out these tasks, we learn from the achievements and share the excitement of the research of the many sponsored scientists and students whose names appear on the papers in the following pages. We also hope that this meeting will enhance your research efforts and will nurture future collaborations and initiatives. We thank all of the researchers whose dedication and innovation have advanced our research and made this meeting possible and, we hope, productive. We also hope that all of you will build on your successes and that we will assemble in two years for our next joint meeting. We thank Diane Marceau of the Chemical Sciences, Geosciences and Biosciences Division for her vital contributions to the administration of our programs, Connie Lansdon of ORISE for meeting logistics, and Dr. Dawn Adin, BES AAAS fellow, for her help in assembling this program. Philip Wilk Larry Rahn iii Agenda Agenda 2013 Separations and Heavy Element Chemistry Principal Investigator's Meeting Gaithersburg Marriott, Washingtonian Center Sunday, April 21 3:00 - 6:00 pm Registration and Setup 6:30 - 7:30 Reception Session 1 Chair - Mark Jensen Materials and Separations 7:30 - 7:45 Wilk, Rahn, A. Clark, Shuh Welcome Selective Recognition of Heavy Elements by Protein- 7:45 - 8:10 Chuan He Based Reagents First Experimentally-Determined Thermodynamic Values 8:10 -8:35 Laetitia Delmau of Francium 8:35- 9:20 Peter Burns EFRC Overview Monday, April 22 8:10 - 8:40 am Continental Breakfast provided 8:40 - 8:55 am John Miller DOE Update Session 2 Chair - Richard Wilson Spectroscopy and Coordination Chemistry Probing the Actinide-Ligand Binding and the Electronic 8:55 - 9:20 Lai Sheng Wang Structure of Gaseous Actinide Molecules and Clusters Using Anion Photoelectron Spectroscopy Investigations into 5f orbital occupancy and radiation 9:20 - 9:45 Corwin Booth damage in actinide intermetallics 9:45 - 10:10 James Ibers Actinide Transition-Metal Chalcogenides and Pnictides 10:10 - 10:40 Break Session 3 Chair - Udo Becker Synthesis and Spectroscopy Keynote Lecture: Recent Progress in the Chemistry of 10:40 - 11:25 Invited - Stephen Liddle Novel Uranium-Ligand Bonds 11:25 - 11:50 David Clark Trends in Orbital Mixing for Actinide-Ligand Bonds Differentiating Between Trivalent Lanthanides and 11:50 - 12:15 Thomas Albrecht-Schmitt Actinides 12:15 - 2:00 pm Working lunch provided iv Session P1 – Poster Session 1 2:00 - 4:00 Binding Anions Selectively with Modular Triazolophanes P1 Amar Flood and Releasing them with Light Molecular Transuranic Discovery Science: Underpinning P3 Andrew Gaunt National Energy Security and Waste Remediation Needs – Early Career Research Program Supramolecular Organization Within Electrolyte P5 Aurora Clark Solutions and the Importance of Molecular Hydrophobicity to Successful Actinide Solvent Extraction P7 David Dixon Understanding Actinide Aggregation American Chemical Society’s Summer School in Nuclear P9 J. David Robertson and Radiochemistry An Integrated Basic Research Program for Advanced P11 James Wishart Nuclear Energy Systems based on Ionic Liquids Fundamental needs in actinide separation science: P13 John Arnold Developing our understanding of covalency through molecular actinide metal–metal bonds Ion Pair Receptors: Fundamental Studies Involving P15 Jonathan Sessler Recognition and Extraction Structured Phases and Electrochemistry at Interfaces in P19 Mark Antonio Separation Science An Integrated Basic Research Program for Advanced P21 Mark Dietz Nuclear Energy Systems based on Ionic Liquids P23 Mark Jensen Multi-Stage Separation of Actinides with Biomolecules Topological Structural Relationships, Cation-Cation P25 Peter Burns Interactions, and Properties of U(VI) and Np(V) Compounds Interfacial Transport and Liquid – Liquid Distribution of P27 Rene Corrales An(III) Complexes Evaluating Actinide-Oxygen Bonding with O K-edge XAS P29 Stosh Kozimor and TDDFT Controlling Actinide Hydration in Mixed Solvent P31 Sue Clark Systems: Towards Tunable Solvent Systems to Close the Nuclear Fuel Cycle P33 Suntharalingam Skanthakumar Electronic Structure and Magnetism in f Ion Materials Exploring the Reactivity of the Uranyl Ion and its P35 Trevor Hayton Chalcogen Analogues: Expanding our Understanding of Uranyl Reactivity and Behavior Fundamental Chemistry of Technetium in Oxide P37 Wayne Lukens Matrices Characterization of f-Orbital Bonding v Session 4 Chair - Trevor Hayton Actinides and Theory Synthetic, Spectroscopic, and Computational Studies of 4:00 - 4:25 Suzanne Bart Redox-Active Uranium Complexes for Fundamental Organometallic Reactions Accurate ab Initio Thermochemistry and Spectroscopy of 4:25 - 4:50 Kirk Peterson Molecules Containing f-block Elements Multiconfigurational Quantum Chemical Study of 4:50 - 5:15 Laura Gagliardi Actinide and Lanthanide Containing Systems 5:15 - 5:30 Break Session 5 Chair - Amar Flood Bonding and Solutions Actinide Solution Chemistry: Thermodynamics and 5:30 - 5:55 Lingfeng Rao Structure of Actinide Complexes in Solution An Integrated Basic Research Program for Advanced 5:55 - 6:20 Sheng Dai Nuclear Energy Systems based on Ionic Liquids Actinyl Compounds with Cation-Cation Interactions 6:20 - 6:45 Gengbang Jin (CCIs) 6:45 - 8:00 Dinner on your own Tuesday, April 23 8:00 - 8:30 am Continental Breakfast provided Session 6 Chair - Wayne Lukens Coordination Chemistry and Separations Principles of Chemical Recognition and Transport in 8:30 - 8:55 am Benjamin Hay Extractive Separations: Molecular Modelling and Design of Ion Receptors Emergent Behavior via Hierarchical Structure in Solvent 8:55 - 9:20 Ross Ellis Extraction Organic Phases Self-Assembled Ionophores and Membrane Active 9:20 - 9:45 Jeffrey Davis Transporters 9:45- 10:15 Break Session 7 Chair - Andrew Gaunt Separations and Coordination Chemistry Keynote Lecture: The TALSPEAK Process: Using 10:15 - 11:00 Invited - Ken Nash Fundamental Chemistry to Unravel Complex Interactions A