On the Nature of the Entropic Bond
Abstract
rties. Partnership between experiment and simulation has yielded tremendous knowledge and insight over 20 years that is now used for, design and synthesis. Yet no theory allowing for rapid, first pri,le, rigorous theory and software packages have been supporting atomic crystal design and structure prediction for decades. Remarkabl,y, nanoparticles and atoms can assemble into identical structures, differing only on length, time and energy scales, suggesting that, a parallel theory may be possible. Nanoparticles can even form these structures via entropic bonding ? a new way of describing the,entropic forces that drive ordering of particles due solely to their shape. Simple shapes self-assemble via entropic bonding into ex,tremely complex structures also seen for atoms, with unit cells containing hundreds of particles. Pursuing the parallels between ent,ropic and electronic bonding of nanoparticles and atoms, respectively, has the potential to transform nanoparticle design and synthe,sis and provide deep, foundational understanding of the relationship between valency and structure applying to all types of material,s building blocks.Our objective is to develop a foundational theory of entropic bonding based on statistical thermodynamics and use,it to discover the fundamental connection between valence and structural complexity in matter. By mapping entropic bonding onto elec,tronic bonding in hundreds of different crystals to relate shapes with atomic elements, we will investigate why and how atomic valen,ce and colloidal particle shape can produce identical, complex crystal structures despite wholly different forces at play. By discov,ering relationships between valency and structure, we seek to expand the Periodic Table of Atomic Elements into a multi-dimensional,Periodic Table of Shapes and develop predictive design rules for crystals of any building blocks. We will generalize entropic bondin,g theory using analytical approaches to include explicit nanoparticle interactions. We will impact DoD capabilities by making this g,eneralized theory available through our open-source software and perform the first ab initio predictions of nanoparticle superlattic,e design. Finally, we aim to gain fundamental insight into entropic forces in biological cells, where the crowding of shapes is prev,alent and entropic bonding is underappreciated. We will develop and test our ideas in a tight theory-modeling-simulation feedback lo,op, validating our work using simulation as well as experimental data from the literature and from collaborators.Anticipated outcome,s include a transformational paradigm shift in our understanding of structural complexity, foundational new knowledge on the entropi,c bond, a new and powerful structure prediction method for colloidal crystals analogous to the electronic structure methods used by,materials scientists for atomic and molecular structure prediction. Potential applications include self-assembled materials for nove,l photonic, plasmonic and mechanical properties, including applications of interest to DoD such as optical microsensing, broadband c,ircular polarizers, quantum information platforms and more. Students and postdocs will be trained in nanoscience, computation, simul,ation, and applications. Foundationally, our project has the potential for transformative impact on science by demonstrating the nov,el, disruptive and paradigm-shifting notion of the entropic bond. If successful, our findings are of the type that will find their w,ay into textbooks alongside the usual chemical bonds we all learn about in kindergarten.Approved for Public Release
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Oct 07, 2022
- Source ID
- N000142212821
Entities
People
- Sharon Glotzer
Organizations
- Board of Regents of the University of Michigan
- Office of Naval Research
- United States Navy