Research | Mayes Group

RESEARCH

The core of our research lies at the intersection of quantum chemistry, molecular simulations, materials modeling, and high-performance computing. A central focus of our efforts is the development of new theories and methods that enable predictive, highly accurate, large-scale ab initio approaches. We also pursue application-driven research, employing advanced computational techniques to understand, simulate, and predict complex chemical and biological processes.

Modeling and Simulation of Electrolytes for Advanced Energy Storage

Predictive computational models can be used to accelerate the material development process. Computational and theoretical chemistry can provide fundamental insights into the structures, properties, and reactivities of molecules. Over the years, my research group has focused on two key area of electrochemical storage: (i) non-aqueous redox flow battery (NRFB) electrolytes and (ii) solid polymer electrolytes for structural energy applications, including flexible and wearable electronics and multifunctional supercapacitors. These technologies are increasingly vital to the transition toward sustainable and resilient energy systems. My research team develops and applies a multiscale computational approach that combines quantum chemical calculations, molecular dynamics simulations, and machine learning to guide the rational design of redox-active species and polymer electrolytes. Recently, we established a computational framework capable of predicting solubility trends in non-aqueous electrolytes. Through this work, we identified lattice free energy, often overlooked in earlier models, as a critical thermodynamic factor influencing solubility. Our findings revealed specific structural features that govern solubility, stability, and ionic transport, thereby enabling the targeted design of next-generation electrolytes. These computational insights have directly informed experimental efforts and are now being advanced through multi-institutional collaborations supported by the National Science Foundation (NSF) and the Office of Naval Research (ONR).

Benjoe Rey B. Visayas, Shyam Pahari, Tulsi Poudel, James Golen, Patrick Cappillino, and Maricris L. Mayes*, “Designing Alkylammonium Cations for Enhanced Solubility of Anionic Active Materials in Redox Flow Batteries: The Role of Bulk and Chain Length”, ChemPhysChem, 25, e202400517(2024). (* front cover ChemPhysChem, 25, e202482401 (2024).)
Benjoe Rey B. Visayas, Shyam K. Pahari, Tugba Ceren Gokoglan, James A. Golen, Ertan Agar, Patrick J. Cappillino, and Maricris L. Mayes*, "Computational and Experimental Investigation of the Effect of Cation Structure on the Solubility of Anionic Flow Battery Active-materials", Chem. Sci. (2021) [selected for 2021 Chemical Science HOT Article collection; selected as Editor’s Choice: Zaiping Guo]
Aysha Siddika Asha, Mubeen Jamal, Simon Gravelle, Maricris L. Mayes, Caiwei Shen, “Exploring the Impact of Minor Water Content on Polymer Electrolytes with Molecular Dynamics”, J. Phys. Chem. B, 129, 1061 (2025).

Molecular-Level Understanding of Peptide Self-Assembly and Nanostructured Biomaterials

My research group investigates how aromatic dipeptides self-assemble into well-defined nanostructures, such as nanotubes and fibrils, with potential applications in biomedicine and materials science. Through quantum chemical calculations, molecular dynamics simulations, and thermodynamic analysis, we have identified the key non-covalent interactions, π–π stacking, hydrogen bonding, and solvent effects, that drive and stabilize these assemblies. Our studies have revealed how subtle changes in peptide sequence or environment influence structural organization and stability. We have also demonstrated that dityrosine-based nanotubes can actively modulate biological behavior. Specifically, our work showed that these nanostructures promote proliferation and differentiation of neuronal PC-12 cells even in the absence of growth factors, suggesting strong potential for use as bioactive scaffolds in tissue engineering, nerve regeneration, and targeted drug delivery. Together, these findings provide a mechanistic foundation for the rational design of peptide-based nanomaterials, advancing their use in regenerative medicine, biosensing, and soft nanotechnology

Prathyushakrishna Macha, Maricris L. Mayes, Benjoe Rey B. Visayas, Vikas, Soni, Vamshi, Sammeta, and Milana Vasudev, “Influence of Dityrosine Nanotubes on the Expression of Dopamine and Differentiation in Neural Cells”, J Mat Chem. B, 9, 3900 (2021).
Benjoe Rey B. Visayas and Maricris L. Mayes*, “Stackable Aromatic Dipeptide Ring Structures toward Nanotube Formation: Thermodynamics and Interactions in Gas-Phase and Solution”, ChemistrySelect, 6, 10839 (2021).
Maricris L. Mayes* and Lisa Perreault, “Probing the Nature of Noncovalent Interactions in Dimers of Linear Tyrosine-based Dipeptides”, ACS Omega, 4, 911-919 (2019).
Prathyushakrishna Macha, Lisa Perreault, Yasaman Hamedani, Maricris L. Mayes, and Milana Vasudev, “Molecular Mechanisms of Tryptophan-Tyrosine Nanostructures and their Influence on Neuronal-like Cells”, ACS Appl. Bio Mater., 1, 1266-1275 (2018).

Modeling Reaction Mechanisms and Excited-State Dynamics

A molecular-level understanding of photoinduced processes is vital to advancing technologies in energy conversion, atmospheric chemistry, and environmental science. My research group combines high-level quantum chemical methods with nonadiabatic dynamics to investigate the fundamental mechanisms governing photodissociation, photoisomerization, and excited-state reactivity in chemically and technologically important systems. We have studied the electron-impact and photodissociation of methane, a prototypical system in plasma-assisted combustion, planetary atmospheres, and interstellar chemistry. Using trajectory surface-hopping combined with multireference methods (e.g., CASSCF), we demonstrated that accurate treatment of nonadiabatic transitions is essential to capturing radical formation pathways, including CH and other fragments implicated in soot formation and hydrocarbon breakdown. Expanding into condensed-phase photochemistry, we investigated the excited-state behavior of pyruvic acid and uncovered how hydrogen bonding and aqueous solvation modulate its photodegradation mechanisms. These insights have implications for its role in atmospheric chemistry and photobiological processes. We have also explored reversible photochromic reactions in spiropyran-merocyanine systems, identifying key excited-state transitions and structural changes that enable their function as molecular switches. Together, these studies contribute to a broader understanding of excited-state molecular dynamics and chemical transformation, offering predictive frameworks that support the design of new photofunctional materials and inform modeling of environmentally relevant photochemical processes.

Michael Dave P. Barquilla and Maricris L. Mayes*, “Role of Hydrogen Bonding in Bulk Aqueous Phase Decomposition, Complexation, and Covalent Hydration of Pyruvic Acid”, Phys. Chem. Chem. Phys. 24, 25151 (2022).
Michael Dave P. Barquilla and Maricris L. Mayes, “A Computational Study of the Effect of Aqueous Solvation on Ground-State Pyruvic Acid Decomposition: Potential Energy Surfaces, Branching Ratios, and Reaction Rates”, AIP Advances 11, 015243 (2021).
Maricris D. Lodriguito, György Lendvay, George Schatz, “Trajectory Surface-Hopping Study of Methane Photodissociation Dynamics”, J. Chem. Phys. 131, 224320 (2009).
Marcin Ziółkowski, Anna Vikár, Maricris L. Mayes, Ákos Bencsura, György Lendvay, and George Schatz, “Modeling the Electron-Impact Dissociation of Methane”, J. Chem. Phys. 137 22A510 (2012).

High-Performance Computing for Large-Scale Simulations

Scalable, high-performance implementations are essential to extend ab initio quantum chemistry methods to complex, realistic systems. Most legacy quantum chemistry codes were not designed to exploit massively parallel architectures. To address this, I contributed to a major effort at Argonne National Laboratory to optimize and benchmark the GAMESS code on Mira, a 10-petaflops IBM Blue Gene/Q supercomputer (786,432 cores), one of the world’s top three systems at the time. We successfully performed fully ab initio molecular dynamics simulations of liquid water using the FMO2-MP2 method on up to 262,144 cores. This work was among the first to demonstrate the feasibility of treating tens of thousands of correlated electrons in large-scale simulations. It also validated the scalability of the fragment molecular orbital method and emphasized the critical role of three-body interactions in accurate modeling of condensed-phase systems. This project marked a significant advance in adapting quantum chemical methods for next-generation supercomputing, paving the way for high-accuracy simulations of biologically and technologically relevant systems at scale.

Spencer Pruitt, Hiroya Nakata, Takeshi Nagata, Maricris L. Mayes, Yuri Alexeev, Graham Fletcher, Dmitri Fedorov, Kazuo Kitaura, and Mark Gordon, “Importance of Three-Body Interactions in Molecular Dynamics Simulations of Water Demonstrated with the Fragment Molecular Orbital Method”, J. Chem. Theory Comput., 12, 1423-1435 (2016).
Maricris L. Mayes, Graham Fletcher, and Yuri Alexeev, “High Accuracy Predictions of the Bulk Properties of Water”, Argonne National Laboratory, Argonnne, IL, ANL/ALCF/ESP-13/17, July 2013.
Maricris L. Mayes, Graham D. Fletcher, and Mark S. Gordon, “Towards Highly Accurate Large-Scale Ab Initio Calculations Using Fragment Molecular Orbital Method in GAMESS”, 2012 Supercomputing, Salt Lake City, Utah, November 10-16, 2012. [peer-reviewed; highly competitive]
Yuri Alexeev, Maricris L. Mayes, Spencer Pruitt, Graham Fletcher, Dmitri Fedorov, and Mark Gordon, “Scalable Ensemble Ab Initio Calculations Using Fragment Molecular Orbital Method in GAMESS”, 2013 Supercomputing, Denver, CO, November 17-22, 2013 [peer-reviewed; highly competitive]

Development of Highly Accurate Quantum Chemistry Methods

One of the central challenges in electronic structure theory is the development of ab initio methods that are both computationally efficient and capable of accurately describing ground- and excited-state potential energy surfaces. My early research addressed this challenge through the development of novel quantum chemical methods based on the coupled-cluster (CC) wavefunction formalism, widely regarded as the gold standard for high-accuracy calculations. I contributed to the formulation and implementation of a family of non-iterative coupled-cluster methods based on multi-reference perturbation theory, known as MMCC/PT. These methods were designed to overcome the practical limitations of conventional multi-reference approaches while maintaining high accuracy for electronically complex systems. Using the diagrammatic and algebraic tools of quantum many-body theory, I developed the theoretical foundations of MMCC/PT and implemented them in fully vectorized computational codes. By introducing recursive diagram factorization techniques and optimizing intermediate generation, I significantly reduced the computational scaling from N^12 to N^9, where N denotes system size. In benchmark cases, this improvement reduced computational time from 30 days to under 5 minutes. The resulting methods not only provided benchmark-quality data for spectroscopic and thermochemical properties but also demonstrated cross-disciplinary impact. For example, our code was successfully applied, without modification, to a nuclear structure calculation of 56Ni, highlighting its utility beyond traditional chemical applications. This work introduced new theoretical strategies to bridge the gap between accuracy and feasibility in quantum chemistry and remains foundational for treating systems with strong electron correlation in both ground and excited states.

Maricris D. Lodriguito, Piotr Piecuch, “Method of Moments of Coupled Cluster Equations Employing Multi-Reference Perturbation Theory Wavefunctions: General Formalism, Diagrammatic Formulation, Implementation, and Benchmark Studies", in: Progress in Theoretical Chemistry and Physics, Vol. 18, "Frontiers in Quantum Systems in Chemistry and Physics", edited by S. Wilson. P. Grout, J. Maruani, G. Delgado-Barrio, and P. Piecuch (Springer, Berlin, 2008) pp. 67-174.
Mihai Horoi, Jeffrey R. Gour, Marta Włoch, Maricris D. Lodriguito, B. Alex Brown, Piotr Piecuch, “Coupled-Cluster and Configuration-Interaction Calculations for Heavy Nuclei", Phys. Rev. Lett. 98, 112501 (2007).
Maricris D. Lodriguito, Karol Kowalski, Marta Włoch, Piotr Piecuch, “Non-Iterative Coupled-Cluster Methods Employing Multi-Reference Perturbation Theory Wave Functions”, J. Mol. Struct: THEOCHEM, 771, 89-104 (2006).
Marta Włoch, Maricris D. Lodriguito, Piotr Piecuch, Jeffrey R. Gour, “Two New Classes of Non-Iterative Coupled-Cluster Methods Derived from the Method of Moments of Coupled-Cluster Equations”, Mol. Phys, 104, 2149-2172 (2006).