The Theoretical Chemistry Section founded in 1979 provides leading-edge theoretical research to guide and augment experimental efforts in the Chemistry Division, NRL, the Navy, and the Nation. This research is made possible by a continual investment in computational capabilities subsequently leveraged to explore advanced materials and chemistry. Some of the developed capabilities have themselves been revolutionary, including seminal work on Density Functional Theory (DFT) for molecular systems used in modern quantum chemistry codes, e.g. GAUSSIAN 16, the development of Reactive Empirical Bond Order (REBO) potentials used in modern molecular dynamics (MD) codes, e.g. LAMMPS, and the development of DFT for Helical Extended Nanostructures (HENS).

In 1992, the Section published the world’s first paper on the electronic properties of single-wall carbon nanotubes. A natural outgrowth of its prior research on electroactive polymers and fullerenes, this work predicted that the nanotubes would exhibit exceptional conducting properties—a prediction subsequently confirmed following the successful synthesis of these revolutionary nanotubes. Carbon nanotubes, which also exhibit exceptional mechanical properties, are today used in a variety of applications, including sheets providing ESD shielding and plastics for electrostatic-assisted painting. In 2016, the value of the global nanotube market was estimated to be over USD 3 Billion.

More recently, the Section has made significant contributions to the understanding of the electronic and transport properties of graphene and graphene nanoribbons. This includes discovering the critical role edge roughness has on transport and the prediction of electrically switchable magnetism along zigzag edges. By applying a developed two-dimensional (2D) quantum transport formalism, it was shown that a line defect in graphene filters charge carriers based on valley, which is a binary degree of freedom in graphene that could potentially be used for information processing. This valley polarization, which was unexpected as graphene is valley-degenerate, helped inspire the field of valleytronics in 2D materials. The Section has proposed that graphene line defects, once better controlled, could also be used in a new type of transistor called the Graphene Resonant Tunneling Transistor.

To meet its mission, the Section manages a broad interdisciplinary research portfolio built on scientific expertise across multiple fields, including condensed matter physics, energetic materials, nanoscience, quantum chemistry, and quantum computing. These efforts provide theory, modeling, and simulations performed on the Section’s high-performance computing (HPC) clusters, as well as at DoD HPC centers.

Selected Publications

2018 Le, N.Q.., C.. E. Ekuma, B.. I. Dunlap, and D.. Gunlycke, "First-Principles Calculations of Sarin Adsorption on Anatase Surfaces", Journal of Physical Chemistry C, vol. 122, pp. 2832-2839, 2018.
2018 Ekuma, C.. E., and D.. Gunlycke, "Optical Absorption in Disordered Monolayer Molybdenum Disulfide", Physical Review B Rapid Communications, vol. 97, issue 201414(R), 2018.
2018 Pushkar, Y.., K.. M. Davis, and M.. Palenik, "Model of the Oxygen Evolving Complex Which is Highly Predisposed to O–O Bond Formation", The Journal of Physical Chemistry Letters, vol. 9, pp. 3525-3531, 2018.
2018 Purdy, A.., R.. J. Butcher, J.. Yesinowski, S.. A. Fischer, D.. Gunlycke, and B.. L. Chaloux, "“Synthesis and Structure of Sn14Cl6(CH2SiMe3)12: Towards Nanoclusters of 4-Coordinate a-Sn", Inorganic Chemistry, vol. 57, pp. 4921-4925, 2018.
2017 Ekuma, C.E.., V.. Dobrosavljevic, and D.. Gunlycke, "First-principles-based method for electron localization: Application to monolayer hexagonal boron nitride", Physical Review Letters, vol. 118, 2017.
2017 Le, N.. Q., and I.. V. Schweigert, "Modeling Electronic Trap States at Interfaces between Anatase Nanoparticles", Journal of Physical Chemistry C, vol. 121, pp. 14254-14260, 2017.
2017 Schweigert, I.. V., and S.. K. Koh-Fallet, "Bimolecular Reactions between Dimethylnitramine and Its Radical Decomposition Products", Journal of Physical Chemistry A, vol. 121, pp. 1545-1553, 2017.
2017 Fischer, S.. A., B.. I. Dunlap, and D.. Gunlycke, "Proton transport through hydrated chitosan-based polymer membranes under electric fields", Journal of Polymer Science Part B, vol. 55, pp. 1103-1109, 2017.
2017 Hu, A.., N.. W. C. Chan, and B.. I. Dunlap, "Orbital angular momentum eigenfunctions for fast and numerically stable evaluations of closed-form pseudopotential matrix elements", Journal of Chemical Physics, vol. 147, issue 074102, 2017.
2017 Palenik, M.C.., and B.. I. Dunlap, "Variationally fitting the total electron-electron interaction", Physical Review B, vol. 18, pp. 8579-8586, 2017.
2017 Wang, Y.., M.. Moses-DeBusk, L.. Stevens, J.. Hu, P.. Zavalij, K.. Bowen, B.. I. Dunlap, E.. R. Glaser, and B.. Eichhorn, "Sb@Ni12@Sb20−/+ and Sb@Pd12@Sb20n Cluster Anions, Where n = +1, −1, −3, −4: Multi-Oxidation-State Clusters of Interpenetrating Platonic Solids", Journal of the American Chemical Society, vol. 139, pp. 619-622, 2017.
2017 Schweigert, I.V.., and D.. Gunlycke, "Hydrolysis of Dimethyl Methylphosphonate by the Cyclic Tetramer of Zirconium Hydroxide", Journal of Physical Chemistry A, vol. 121, pp. 7690-7696, 2017.
2016 Palenik, M.. C., and B.. I. Dunlap, "General Degeneracy in Density Functional Perturbation Theory", Physical Review B, vol. 96, issue 045109, 2016.
2016 Gunlycke, D.., and F.. Tseng, "Triangular lattice exciton model", Physical Chemistry Chemical Physics, vol. 18, pp. 8579-8586, 2016.
2016 Tseng, F.., E.. Simsek, and D.. Gunlycke, "Using dark states for exciton storage in transition-metal dichalcogenides", Journal of Physics Condensed Matter, vol. 23, issue 034005, 2016.
2016 Palenik, M.C.., and B.. I. Dunlap, "Degenerate density perturbation theory", Physical Review B, vol. 94, issue 115108, 2016.
2016 Jia, Q.., J.. Li, K.. Caldwell, D.. E. Ramaker, J.. M. Ziegelbauer, R.. S. Kukreja, A.. Kongkanand, and S.. Mukerjee, "Circumventing Metal Dissolution Induced Degradation of Pt-Alloy Catalysts in Proton Exchange Membrane Fuel Cells: Revealing the Asymmetric Volcano Nature of Redox Catalysis", ACS Catalysis, vol. 6, pp. 928-938, 2016.
2016 Patridge, C.J.., C.. T. Love, and D.. E. Ramaker, "C.J. Utilization of heavy alkali dopants as a beacon to study the cathode electrolyte decomposition layer in lithium-ion batteries", Ionics, vol. 22, pp. 51-62, 2016.
2015 Schweigert, I.. V., "Ab Initio Molecular Dynamics of High-Temperature Unimolecular Dissociation of Gas-Phase RDX and Its Dissociation Products", Journal of Physical Chemistry A, vol. 119, pp. 2747-2759, 2015.
2015 Palenik, M.C.., and B.. I. Dunlap, "Density Perturbation Theory", Journal of Chemical Physics, vol. 143, issue 044115, 2015.
2015 Gunlycke, D.., and C.. T. White, "Probing barrier transmission in ballistic graphene", Physical Review B, vol. 91, issue 075425, 2015.
2015 Miller, S.. P., B.. I. Dunlap, and A.. S. Fleischer, "Dopant Clustering and Correlated Oxygen Migration in Conditionally Stabilized Zirconia Electrolytes", Journal of Fuel Cell Science and Technology, vol. 12, issue 021003, 2015.
2015 Mukherjee, B.F.., F.. Tseng, D.. Gunlycke, K.. K. Amara, G.. Eda, and E.. Simsek, "Complex electrical permittivity of the monolayer molybdenum disulfide (MoS2) in near UV and visible", Optical Materials Express, vol. 5, issue 447-455, 2015.
2014 Zhakhovsky, I.. V., M.. M. Budzevich, A.. C. Landerville, I.. I. Oleynik, and C.. T. White, "Laminar, cellular, transverse, and multiheaded pulsating detonations in condensed phase energetic materials from molecular dynamics simulations", Physical Review E, vol. 90, issue 033312, 2014.
2014 Gunlycke, D.., and C.. T. White, "Specular graphene transport barrier", Physical Review B, vol. 90, issue 035452, 2014.
2014 Brennan, J.K.., M.. Lisal, J.. D. Moore, S.. Izvekov, I.. V. Schweigert, and J.. P. Larentzos, "Coarse-Grain Model Simulations of Nonequilibrium Dynamics in Heterogeneous Materials", Journal of Physical Chemistry Letters, vol. 5, pp. 2144-2149, 2014.
2014 Zhakhovsky, V.. V., N.. A. Inogamov, B.. J. Demaske, I.. I. Oleynik, and T.. White, "Elastic-plastic collapse of super-elastic shock waves in face-centered-cubic solids", Journal of Physics Conference Series, vol. 500, issue 172007, 2014.
2014 Zhakhovsky, V.. V., M.. M. Budzevich, A.. C. Landerville, I.. I. Oleynik, and C.. T. White, "From laminar to turbulent detonantions in energetic materials from molecular dynamics simulations", Journal of Physics Conference Series, vol. 500, issue 172005, 2014.
2014 Schweigert, I.. V., "Quantum Mechanical Simulations of Condensed-Phase Decomposition Dynamics in Molten RDX", Journal of Physics Conference Series, vol. 500, issue 052039, 2014.
2014 Zhakhovsky, V.. V., M.. M. Budzevich, A.. C. Landerville, I.. I. Oleynik, and C.. T. White, "Nano-scale spinning detonation in a condensed phase energetic material", Journal of Physics Conference Series, vol. 500, issue 172006, 2014.