Issue 13, 2024

IR spectroscopic characterization of 3d transition metal carbene cations, FeCH2+ and CoCH2+: periodic trends and a challenge for DFT approaches

Abstract

A combination of IR multiple-photon dissociation (IRMPD) action spectroscopy and quantum chemical calculations was employed to investigate the [M,C,2H]+ (M = Fe and Co) species. These were formed by reacting laser ablated M+ ions with oxirane (ethylene oxide, c-C2H4O) in a room temperature ion trap. IRMPD spectra for the Fe and Co species are very similar and exhibit one major band. Comparison with density functional theory (DFT) and coupled cluster with single and double excitations (CCSD) calculations allows assignment of the spectra to MCH2+ carbene structures. For these 3d transition metal systems, experimental IRMPD spectra compare relatively poorly with DFT calculated IR spectra, but CCSD calculated spectra are a much better match primarily because the M–C stretch gains significant intensity. The origins of this behavior are explored in some detail. The present results are also compared to previous results for the 4d and 5d congeners and the periodic trends in these structures are evaluated.

Graphical abstract: IR spectroscopic characterization of 3d transition metal carbene cations, FeCH2+ and CoCH2+: periodic trends and a challenge for DFT approaches

Supplementary files

Article information

Article type
Paper
Submitted
03 yan 2024
Accepted
07 fev 2024
First published
07 fev 2024
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2024,26, 9948-9962

IR spectroscopic characterization of 3d transition metal carbene cations, FeCH2+ and CoCH2+: periodic trends and a challenge for DFT approaches

F. J. Wensink, C. E. Smink, P. B. Armentrout and J. M. Bakker, Phys. Chem. Chem. Phys., 2024, 26, 9948 DOI: 10.1039/D4CP00026A

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