Microhydration of the metastable N-Protomer of 4-Aminobenzoic acid by condensation at 80 K: H/D exchange without conversion to the more stable O-protomer

Khuu, Thien; Stropoli, Santino James; Greis, Kim; Yang, Nan; Johnson, Mark A.

doi:10.1063/5.0119027

Title: Microhydration of the metastable N-Protomer of 4-Aminobenzoic acid by condensation at 80 K: H/D exchange without conversion to the more stable O-protomer

Journal Article · Tue Sep 06 00:00:00 EDT 2022 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0119027· OSTI ID:1885568

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Yale Univ., New Haven, CT (United States)
Fritz Haber Inst. of the Max Planck Society (Germany)

4-Aminobenzoic acid (4ABA) is a model scaffold for studying solvent-mediated proton transfer. Although protonation at the carboxylic group (O-protomer) is energetically favored in the gas phase, the N-protomer, where the proton remains on the amino group, can be kinetically trapped by electrospray ionization of 4ABA in an aprotic solvent such as acetonitrile. Here we report the formation of the hydrated deuterium isotopologues of the N-protomers, RND₃⁺·(H₂O)_n=1-3, (R=C₆H₄COOD), which are generated by condensing water molecules onto the bare N-protomers in a liquid nitrogen cooled, radiofrequency octopole ion trap at 80 K. The product clusters are then transferred to a 20 K cryogenic ion trap where they are tagged with weakly bound D₂ molecules. The structures of these clusters are determined by analysis of their vibrational patterns obtained by resonant IR photodissociation. The resulting patterns confirm that the metastable N-protomer configuration remains intact even when warmed by sequential condensation of water molecules. Attachment of H₂O molecules onto the RND₃⁺ head group also affords the opportunity to explore the possibility of H/D exchange between the acid scaffold and the proximal water network. The spectroscopic results establish that although the RND₃⁺·(H₂O)_n=1,2 clusters are formed without H/D exchange, the n = 3 cluster exhibits about 10% H/D exchange as evidenced by the appearance of the telltale HOD bands. Furthermore, the site of exchange on the acid is determined to be the acidic OH by the emergence of the OH stretching fundamental in the -COOH motif.

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Research Organization:: Yale Univ., New Haven, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021012

OSTI ID:: 1885568

Journal Information:: Journal of Chemical Physics, Vol. 157, Issue 13; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Intermolecular proton translocation
cryogenic ion chemistry
vibrational spectroscopy
isotope exchange
mass spectrometry
photofragmentation
4-Aminobenzoic acid
para-Aminobenzoic acid
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Title: Microhydration of the metastable N-Protomer of 4-Aminobenzoic acid by condensation at 80 K: H/D exchange without conversion to the more stable O-protomer

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