Reaction Dynamics in Extreme Environments:Matrix Isolation of Impossible Molecules
Marks, J. H.,1,2 Eckhardt, A. K.,3 Bai, X.,4 Nikolayev, A. A.,5 Wang, J.,1,2 Turner, A. M.,1,2Yang, T.,4 Fortenberry, R. C.,6 Mebel, A. M.,7 Kaiser, Ralf I.1,2*
ralfk@hawaii.edu
Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822, USAW. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, HI 96822,
USA
3Lehrstuhl für Organische Chemie II, Ruhr-Universität Bochum, 44801 Bochum, Germany
4
State Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai 200062, P. R. China
5
Samara National Research University, Samara 443086, Russia
6
Department of Chemistry & Biochemistry, University of Mississippi, MS 38677, USA
7
Department of Chemistry and Biochemistry, Florida International University, Miami,
FL 33199, USA
1

2Ice coated interstellar nanoparticles have materialized as molecular factories in the synthesis ofcomplex, often biorelevant organics in cold molecular clouds and star-forming regions. An intimate understanding of the fundamental reaction mechanisms leading to these organics in deep
space requires new knowledge on the processing of low temperature ices by (non)ionizing radiation present even deep inside cold molecular clods. This talk provides an overview on recent
surface science and matrix isolation of particular importance in deciphering the underlying reaction
dynamics and kinetics leading to complex organics in deep space, many of which should not exist
according to classical textbook knowledge. In detail, this talk reports on the preparation andidentification of the highly ring-strained oxirene molecule (c-C2H2O) via resonant energy transferof the internal energy of oxirene to the vibrational modes of the matrix molecules,[1] on the synthesis of the homologues series of disubstituted methane molecules [methanediamine(CH2(NH2)2),[2] aminomethanol (NH2CH2OH),[3] methanediol (CH2(OH)2)[4]], and the previously
elusive methanetriol (CH(OH)3) — the simplest orthocarboxylic acid — along with its isomers
hydroxyperoxymethane (CH3OOOH) and hydroxyperoxymethanol (CH2(OH)OOH). Supported
by electronic structure calculations, these molecules were identified in the gas-phase upon sublimation from the icy matrices via isomer-selective photoionization reflectron time-of-flight mass
spectrometry combined with isotopic substitution studies and detection of photoionization
fragments.[5][1]J. Wang, J. H. Marks, A. M. Turner, A. M. Mebel, A. K. Eckhardt, R. I. Kaiser, Gas-Phase
Detection of Oxirene, Sci. Adv, 9, eadg1134 (2023).
[2]
J. H. Marks, J. Wang, R. C. Fortenberry, R. I. Kaiser, Preparation of methanediamine(CH2(NH2)2) - A precursor to nucleobases in the interstellar medium, Proceedings of theNational Academy of Sciences USA, 119, e2217329119 (2022).
[3]
S. K. Singh, C. Zhu, J. L. Jeunesse, R. C. Fortenberry, R. I. Kaiser, Experimental
Identification of Aminomethanol (NH2CH2OH) – The Key Intermediate in the Strecker
Synthesis, Nat. Commun. 13, 375 (2022).
[4]
C. Zhu, N. F. Kleimeier, A. M. Turner, S. K. Singh, R. C. Fortenberry, R. I. Kaiser, Synthesisof methanediol [CH2(OH)2]: The simplest geminal diol, Proceedings of the National Academyof Sciences USA, 119, e2111938119 (2022).
[5]
A. M. Turner, R. I. Kaiser, Exploiting Photoionization Reflectron Time-of-Flight Mass
Spectrometry to Explore Molecular Mass Growth Processes to Complex Organic Molecules inInterstellar and Solar System Ice Analogs , Acc. Chem. Res., 53, 2791-2805 (2020).