Kirill Prozument

Experimental Physical Chemistry

Biography

2019–present: Chemist, Argonne National Laboratory
2015–2019: Assistant Chemist, Argonne National Laboratory
Postdoctoral researcher (2013–2014) with Prof. Arthur. G. Suits, Wayne State University
Postdoctoral researcher (2007–2012) with Prof. Robert W. Field, Massachusetts Institute of Technology
Ph.D. (2007) and M.S. (2003) in Chemistry from University of Southern California under the guidance of Prof. Andrey F. Vilesov
M.S. (2000) and B.S. (1998) in Applied Mathematics and Physics from the Moscow Institute of Physics and Technology

Research interests

I am interested in discovering fundamental mechanisms of chemical reactions in the gas phase. How and why do molecules react? What are the ways of steering the outcome of their reactions? Can we rationally design new fuels or improve the biomass conversion processes? These questions can be answered by a combination of the experiments that I am conducting using the chirped-pulse Fourier transform millimeter-wave (CP-FTmmW) spectroscopy, and theory and modeling from my colleagues. In particular, we are investigating the contributions from the roaming radicals dynamics, non-thermal effects, quantum tunneling, and H-atom addition/elimination to the outcomes of chemical reactions in different experimental environments.

Pyrolysis and oxidation reactions

In this research direction, complex networks of chemical reactions are thermally initiated in the pyrolysis microreactor [6] or in a newly developed SiO₂/SiC oxidation microreactor,[4] heated to 1000–1800 K. The reaction products are cooled in the supersonic expansion to 5 K where they are detected and quantified using CP-FTmmW spectroscopy. Based on these measurements, and with the help of kinetic modeling, reaction networks are built, and new chemical pathways are discovered.[1]

Time-Resolved Kinetic Chirped-Pulse (TReK-CP) spectroscopy

In this novel experimental approach, chemistry in a room temperature flow-tube reactor is initiated by UV laser pulses.[9] Subsequent reactions and thermalization of energized photo-products are observed in situ with a time- and vibrational quantum state-resolved TReK-CP spectroscopy. Terminal vibrational population distributions (VPDs) of reaction products have been used to understand properties of transition states.[7] Currently, we investigate dissociation reactions in real time by tracing nascent photoproducts as they form in various vibrational states, where the VPD is a function of time.

Assignment of rotational spectra using artificial neural networks

The substantial spectroscopic data flow from CP-FTmmW experiments presents new opportunities for chemical research. At the same time, assignment of broadband rotational spectra and identification of chemical species becomes a bottleneck. We have demonstrated that trained artificial neural networks can recognize patterns in rotational spectra and predict rotational constants of unknown species.[8] The current challenges are i) recognizing multiple species in a mixture, and ii) relating rotational constants to molecular geometries, i.e. solving the inverse problem in spectroscopy.[3]

Recent publications

[1] Rizalina T. Saragi, Nathan A. Seifert, Raghu Sivaramakrishnan, and Kirill Prozument,
“Thermally Initiated Formation of Criegee Intermediate CH₂OO in the Oxidation of
Ethane”, J. Phys. Chem. Lett. 15, 12441−12448 (2024)

[2] Kacee L. Caster, Nathan A. Seifert, Branko Ruscic, Ahren W. Jasper, and Kirill
Prozument, Dynamics of HCN, HNC, and HNCO Formation in the 193 nm
Photodissociation of Formamide, J. Phys. Chem. A 128, 7761−7771 (2024)

[3] Marcus Schwarting, Nathan A. Seifert, Michael J. Davis, Ben Blaiszik, Ian Foster, and
Kirill Prozument, “Twins in rotational spectroscopy: Does a rotational spectrum
uniquely identify a molecule?” J. Chem. Phys. 161, 044309 (2024)

[4] Nathan A. Seifert, Branko Ruscic, Raghu Sivaramakrishnan, and Kirill Prozument, “The
C₂H₄O isomers in the oxidation of ethylene”, J. Mol. Spectrosc. 398, 111847 (2023)

[5] Nathan A. Seifert, Kirill Prozument, and Michael J. Davis, “Computational optimal
transport for molecular spectra: The semi-discrete case”, J. Chem. Phys. 156, 134117
(2022)

[6] Daniel P. Zaleski, Raghu Sivaramakrishnan, Hailey R. Weller, Nathan A. Seifert, David H. Bross, Branko Ruscic, Kevin B. Moore III, Sarah N. Elliott, Andreas V. Copan, Lawrence B. Harding, Stephen J. Klippenstein, Robert W. Field, and Kirill Prozument, “Substitution Reactions in the Pyrolysis of Acetone Revealed through a Modeling, Experiment, Theory Paradigm”, J. Am. Chem. Soc. 143, 3124–3142 (2021)

[7] Kirill Prozument, Joshua H. Baraban, P. Bryan Changala, G. Barratt Park, Rachel G. Shaver, John S. Muenter, Stephen J. Klippenstein, Vladimir Y. Chernyak, and Robert W. Field, “Photodissociation transition states characterized by chirped pulse millimeter wave spectroscopy”, Proc. Natl. Acad. Sci. U.S.A. 117, 146−151 (2020)

[8] Daniel P. Zaleski and Kirill Prozument, “Automated assignment of rotational spectra using artificial neural networks”, J. Chem. Phys. 149, 104106 (2018)

[9] Daniel P. Zaleski, Lawrence B. Harding, Stephen J. Klippenstein, Branko Ruscic, and Kirill Prozument, “Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room Temperature Flow Reactor“, J. Phys. Chem. Lett. 8, 6180−6188 (2017)

[10] Daniel P. Zaleski, Chuanxi Duan, Miguel Carvajal, Isabelle Kleiner, and Kirill
Prozument, “The Broadband Rotational Spectrum of Fully Deuterated Acetaldehyde
(CD₃CDO) in a CW Supersonic Expansion”, J. Mol. Spectrosc. 342, 17−24 (2017)

Complete list of publications at ORCiD