We are actively pursuing the development of methodologies for simplifying the analysis of electronic structure. One objective is refinement of well-known chemical descriptors/heuristics, for example atomic radii and atomic electronegativity, as well as their expansion (through computational means) to high pressure conditions.
We are also developing “Experimental Quantum Chemistry” (EQC), a theoretical framework and a kind of Energy Decomposition Method for analyzing chemical transformations. The EQC method’s unique advantage is that it interchangeably allows for studies of chemical bonds using both quantum mechanically calculated and experimentally measured data.
Conceptual Method Development
Understanding the connection between electronic structure and material properties is a principal challenge in chemistry and material science. Useful insights into chemical bonding allow for “chemical intuition”, which guides and dramatically accelerates experimental efforts.
We are particularly interested in the development of universally applicable chemical descriptors, and methods capable of analyzing chemical bonding in molecules, in extended forms of matter (polymers and crystals), and in matter under high compression. To that end, we are developing ”Experimental Quantum Chemistry”, a unique framework through which the energy of any transformation (such as a bond formation) is described as a sum of terms, all of which can all be interchangeably obtained by experimental or computational means. Other interests include quantification of electron localization, the refinement and furthering of atomic and group electronegativity, and estimates of atomic and effective group radii.
In addition to facilitating for chemical rationales across different fields of disciplines and thermodynamic conditions (high pressure, low temperature, long time-scales), our research is generating promising input data for future machine learning approaches aimed at high throughput material discovery.
- M. Rahm, T. Zeng, R. Hoffmann, Electronegativity Seen as the Ground State Average Valence Electron Binding Energy, J. Am. Chem. Soc, 141,342-351, 2019 [A new scale of electronegativity]
- M. Rahm, R. Cammi, N. W. Ashcroft, R. Hoffmann, Squeezing all Elements in the Periodic Table: Electron Configuration and Electronegativity of the Atoms under Compression, J. Am. Chem. Soc.,141, 10253-10271, 2019 [The Periodic Table at 0-300 GPa]
- M. Rahm, R. Hoffmann, Distinguishing Bonds, J. Am. Chem. Soc., 138, 3731-3744, 2016 [Introduction to the Q-descriptor, shown in figure]
- M. Rahm, R. Hoffmann, N.W. Ashcroft, Atomic and Ionic Radii of Elements 1-96, Chem. Eur. J. 22, 14625-14632, 2016
- M. Rahm, R. Hoffmann, Toward an Experimental Quantum Chemistry: Exploring a New Energy Partitioning, J. Am. Chem. Soc., 137, 10282–10291, 2015
What is the molecular basis of life, and how did life originate? These are fundamental questions that ultimately will involve systems of extreme complexity. To help evaluate which initial chemistry might have given rise to such complexity, we are studying one of the Universe’s simplest and most ubiquitous molecules.
Hydrogen cyanide, HCN, is believed to be a key ingredient for prebiotic chemistry, and a versatile building block for the construction of biomolecules. However, the chemical structure of HCN-based polymers remains an open question. There are significant challenges associated with the characterization of polymeric HCN, and highly complex mixtures of soluble and insoluble materials are typically generated in laboratories.
To tackle this challenge, we are using a combination quantum chemistry and theoretical condensed matter physics methodology to explore well-defined HCN-based materials and polymerization mechanisms. It is possible that such structures might form under kinetic controlled conditions (low temperature) and over long time-scales. To evaluate how HCN chemistry plays into observations we are collaborating with planetary scientists, whose particular focus is Saturn’s moon Titan. Titan can, in some respects, be considered a frozen over version of the early Earth, and the former provides a natural laboratory for studying prebiotic chemistry occurring under cryogenic conditions. One of the most abundant products of Titan’s atmospheric chemistry is HCN, where it contributes to the formation of not yet well-understood photochemical hazes.
- H. Sandström, M. Rahm, Can Polarity-inverted Membranes Self-Assemble on Titan?, Sci. Adv. 6, eaax0272, 2020
- M. Rahm, J. I. Lunine, D. A. Usher, D. Shalloway, Polymorphism and Electronic Structure of Polyimine and its Potential Significance for Prebiotic Chemistry on Titan, PNAS, 113, 8121-8126, 2016
- H. E. Maynard-Casely, R. Hodyss, M. L. Cable, T. H. Vub, M. Rahm, A co-crystal between benzene and ethane, an potential evaporite material for Saturn’s moon Titan, IUCrJ, 3, doi:10.1107/S2052252516002815, 2016