Conformer-Specific Photoelectron Spectroscopy of Carbonic Acid: H2CO3

Keisuke Kanayama; Hisashi Nakamura; Kaoru Maruta; Andras Bodi; Patrick Hemberger

doi:10.1021/acs.jpclett.4c00343

Conformer-Specific Photoelectron Spectroscopy of Carbonic Acid: H₂CO₃

J Phys Chem Lett. 2024 Mar 14;15(10):2658-2664. doi: 10.1021/acs.jpclett.4c00343. Epub 2024 Mar 1.

Authors

Keisuke Kanayama^{1

2

3}, Hisashi Nakamura², Kaoru Maruta², Andras Bodi¹, Patrick Hemberger¹

Affiliations

¹ Laboratory for Synchrotron Radiation and Femtochemistry, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland.
² Institute of Fluid Science, Tohoku University 2-1-1 Katahira, Aoba, Sendai, Miyagi 980-8577, Japan.
³ Graduate School of Engineering, Tohoku University, 6-6 Aramaki Aza Aoba, Aoba, Sendai, Miyagi 980-8579, Japan.

Abstract

Carbonic acid (H₂CO₃) is a fundamental species in biological, ecological, and astronomical systems. However, its spectroscopic characterization is incomplete because of its reactive nature. The photoionization (PI) and the photoion mass-selected threshold photoelectron (ms-TPE) spectra of H₂CO₃ were obtained by utilizing vacuum ultraviolet (VUV) synchrotron radiation and double imaging photoelectron photoion coincidence spectroscopy. Two carbonic acid conformers, namely, cis-cis and cis-trans, were identified. Experimental adiabatic ionization energies (AIEs) of cis-cis and cis-trans H₂CO₃ were determined to be 11.27 ± 0.02 and 11.18 ± 0.03 eV, and the cation enthalpies of formation could be derived as Δ_fH°_0K = 485 ± 2 and 482 ± 3 kJ mol^-1, respectively. The cis-cis conformer shows intense peaks in the ms-TPES that are assigned to the C=O/C-OH stretching mode, while the cis-trans conformer exhibits a long progression to which two C=O/C-OH stretching modes contribute. The TPE spectra allow for the sensitive and conformer-selective detection of carbonic acid in terrestrial experiments to better understand astrochemical reactions.