The Huo group develops new theoretical approaches to investigate chemical reactivities when they are enabled by intrinsically quantum mechanical behavior. These Quantum mechanical behaviors, such as the quantum tunneling of a proton and strong coupling to a quantized photon, has shown great promise in enabling new paradigms for chemical transformations that will profoundly impact catalysis, energy production, and the field of chemistry at large. Understanding the real-time dynamics of these processes will inspire transformative design principles that take advantage of intrinsic quantum behaviors and facilitate the quantum leap of chemistry. Accurately and efficiently simulating non-adiabatic transitions among these quantized electronic, vibronic, photonic, or hybridized states remains a central challenge in theoretical chemistry. My group works to address this challenge by developing new quantum dynamics approaches that accurately simulate these processes and provide critical insights into these new phenomena.
Develop New Theoretical Approaches for Quantum Dynamics Simulations. Accurately and efficiently performing quantum dynamics simulation remains a central challenge in theoretical chemistry. The dynamics aspect of this challenge boils down to two parts: (i) a lack of efficient approaches that can accurately describe electronic non-adiabatic effects and nuclear quantum effects, (ii) the discrepancy between quantum dynamics methods and electronic structure approaches because they are usually developed in two different representations. We are actively developing new theoretical approaches that explicitly address these long-standing fundamental challenges. Through these new developments, we aim to significantly expand the scope and applicability of quantum dynamics simulations and bridge the electronic structure and quantum dynamics communities through a transformative platform.
Explore New reactivities Enabled byQuantum Electrodynamics. Coupling molecules to the quantized radiation field in an optical cavity has shown great promise for new chemical reactivities. The resulting photon-matter hybrid states, so-called polaritons, can significantly change the shape of the potential energy surface and open up new possibilities to control chemical transformations. The non-adiabatic dynamics of such hybrid molecule-field systems, however, remains unclear and beyond the usual paradigm of photochemistry which does not include quantized photon as part of the system, or quantum optics which focus on studying atoms rather than molecules. We are developing new theoretical approaches beyond the available tools in the quantum optics or photochemistry to simulate polaritonic non-adiabatic dynamics, and investigating the fundamental principles of the polariton enhanced photochemistry. We aim to explore the possibility of tuning chemical reactions through fundamental quantum light-matter interactions by changing the photon frequencies or the molecule-cavity coupling strength.
Investigate Photochemical Reactions in Solar Energy Conversions. We are investigating solar energy conversion processes to obtain detailed mechanistic insights. Such dynamical insights, which have been historically overlooked by studies employing static electronic structure calculations, will inspire new design principles for next-generation solar technology. Currently, we focus on investigating photoinduced proton-coupled electron transfer reactions, which play a crucial role in solar fuel production processes because they allow efficient transfer of electrons and protons, the most fundamental reactions that are at the center of many solar energy conversion applications. Through direct quantum dynamics simulations and experimental collaborations, we aim to obtain critical insights into these primary photochemical reactions that are at the center of solar energy conversion and provide new design principles to predict and control the reactivities of next-generation photocatalysts.
- Li, A. Mandal, and P. Huo, “Theory of Mode-Selective Chemistry through Polaritonic Vibrational Strong Coupling”, J. Phys. Chem. Lett. 12, 6974-6982 (2021).
- M. Weight, A. Mandal, and P. Huo, “Ab-initio Symmetric Quasi-Classical Approach to Investigate Molecular Tully Models”, J. Chem. Phys. 155, 084106 (2021).
- H. Farag, A. Mandal and P. Huo, “Polariton Induced Conical Intersection and Berry Phase”, Phys. Chem. Chem. Phys. 23, 16868-16879 (2021).
- X. Li and P. Huo, “Investigating Tunneling Controlled Chemical Reactions Through ab-initio Ring Polymer Molecular Dynamics”, (selected for a supplementary journal cover), J. Phys. Chem. Lett. 12, 6714-6721 (2021)
- L. Qiu, A. Mandal, O. Morshed, M. T. Meidenbauer, W. Girten, P. Huo, A. N. Vamivakas and T. D. Krauss, “Molecular Polaritons Generated from Strong Coupling between CdSe Nanoplatelets and a Dielectric Optical Cavity” (selected for a supplementary journal cover), J. Phys. Chem. Lett. 12, 5030 (2021).
- D. Bossion, S. Chowdhury and P. Huo, “Non-Adiabatic Ring Polymer Molecular Dynamics with Spin Mapping Variables”, J. Chem. Phys. J. Chem. Phys. 154, 124124 (2021).
- S. Chowdhury and P. Huo, “Non-adiabatic Matsubara Dynamics and Non-adiabatic Ring Polymer Molecular Dynamics”. (Invited article for the J. Chem. Phys. “Emerging Investigator” Special Issue) J. Chem. Phys. 154, 124124 (2021).
- X. Li, A. Mandal and P. Huo, “Cavity Frequency-Dependent Theory for Vibrational Polariton Chemistry”, (selected for Editors’ Highlights) Nat. Comm.12, 1315 (2021).
- S. Chowdhury, A. Mandal, and P. Huo, “Ring-Polymer Quantization of Photon Field in Polari- ton Chemistry”, J. Chem. Phys. 154, 044109 (Invited article for the J. Chem. Phys. “Polariton Chemistry” Special Issue) (2021).
- S. S. Yamijala and P. Huo, “Direct Non-adiabatic Simulations of the Photoinduced Charge Transfer Dynamics”, J. Phys. Chem. A, 125, 628-635 (Invited article for the “Josef Michl Festschrift”) (2021).
- A. Mandal, S. M. Vega and P. Huo, “Polarized Fock States and the Dynamical Casimir Effect in Molecular Cavity Quantum Electrodynamics”, (selected for a supplementary journal cover) J. Phys. Chem. Lett. 11, 9215 (2020).
- M. A. D. Taylor, A. Mandal, W. Zhou and P. Huo,“Resolution of Gauge Ambiguities in Molecular Cavity Quantum Electrodynamics”, Phys. Rev. Lett. 125, 123602 (2020).
- A. Mandal, T. D. Krauss and P. Huo, “Polariton Mediated Electron Transfer via Cavity Quantum Electrodynamics” J. Phys. Chem. B. 124, 6321-6340 (2020).
- W. Zhou, A. Mandal and P. Huo, “Quasi-Diabatic Scheme for Non-adiabatic On-the-fly Simulation”, J. Phys. Chem. Lett. 10, 7062 (2019).
- A. Mandal and P. Huo, “Investigating New Reactivities Enabled by Polariton Photochemistry”, (Highlighted as the most highly cited articles in 2019 and 2020, selected as part of the Polaritons in Physical Chemistry virtual issue) J. Phys. Chem. Lett. 10, 5519-5529 (2019).
- S. Chowdhury and P. Huo, “State Dependent Ring Polymer Molecular Dynamics for Investigating Excited Nonadiabatic Dynamics”, J. Chem. Phys. 150, 244102 (Invited article for the “Dynamics of Open Quantum Systems” Special Issue). (2019).
- A. Mandal, J. S. Sandoval, F. A. Shakib and P. Huo, “Quasi Diabatic Propagation Scheme for Direct Simulation of Proton-Coupled Electron Transfer Reaction”, J. Phys. Chem. A 123, 2470, (Invited article for the “Young Scientists” Special Issue) (2019).
- J. S. Sandoval, A. Mandal and P. Huo, “Symmetric Quasi Classical Dynamics with Quasi Diabatic Propagation Scheme”, J. Chem. Phys. 149, 044115 (2018).
- A. Mandal, F. A. Shakib and P. Huo, “Investigating Photoinduced Proton Coupled Electron Transfer Reaction using Quasi Diabatic Dynamics Propagation”, J. Chem. Phys. 148, 244102 (2018).
- A. Mandal, S. S. Yamijala, and P. Huo, “Quasi-Diabatic Representation for Non-Adiabatic Quantum Dynamics Propagation”, J. Chem. Theory Comput. 14, 1828 (2018).
- S. Chowdhury and P. Huo, “Coherent State Mapping Ring-Polymer Molecular Dynamics for Non- Adiabatic Quantum Propagations”, J. Chem. Phys. 147, 214109 (2017).
- F. A. Shakib and P. Huo, “Ring Polymer Surface-Hopping: Incorporating Nuclear Quantum Effects Into Non-Adiabatic Molecular Dynamics Simulations”, J. Phys. Chem. Lett. 8, 3073 (2017).
- M. Castellanos and P. Huo, “Enhancing Singlet-Fission Dynamics by Suppressing Destructive Interference between Charge-Transfer Pathways”, J. Phys. Chem. Lett. 8, 2480 (2017).