Electronic structure of ph2-containing complexes as photoelectron spectroscopy candidates

Document Type

Journal Article

Publication Title

Computational and Theoretical Chemistry

Publisher

Elsevier

School

School of Science

RAS ID

60160

Funders

Center for Materials Crystallography at Aarhus University in Denmark / Danish National Research Foundation / Rowe Scientific Vacation Scholarship, Australia

Comments

Watson, P. D., Summers, A. M., McKinley, A. J., & Wild, D. A. (2023). Electronic structure of ph2-containing complexes as photoelectron spectroscopy candidates. Computational and Theoretical Chemistry, 1222, article 114054. https://doi.org/10.1016/j.comptc.2023.114054

Abstract

Phosphine is attracting interest due to the role it plays in extraterrestrial and interplanetary atmospheric environments. Phosphorus hydride anion and neutral van der Waals complexes with CH4, C2H4, HCCH, CO2, H2S and NH3 have been investigated as potential targets for photoelectron spectroscopy using a combination of DSD-PBEP86-D3BJ optimised geometries, W2w energies and Franck–Condon simulations. All anion complexes exhibit hydrogen-bonding interactions and while complexes with CH4 are weakly bound, showing minimal perturbation upon complexation. All other solvating molecules studied yield sufficient energetic or vibrational structural differences to be differentiable in photoelectron spectra. Most notably, PH2−CO2 undergoes barrierless nucleophilic addition to form the phosphino formate anion (PH2COO−) and is proposed as one such potential atmospheric sink.

DOI

10.1016/j.comptc.2023.114054

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