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Title: Adiabatic ionization energies of RuC, RhC, OsC, IrC, and PtC
The ionization energies (IEs) of RuC, RhC, OsC, IrC, and PtC are assigned by the measurement of their two-photon ionization thresholds. Although late transition metal–carbon bonds are of major importance in organometallic chemistry and catalysis, accurate and precise fundamental thermochemical data on these chemical bonds are mainly lacking in the literature. Based on their two-photon ionization thresholds, in this work, we assign IE(RuC) = 7.439(40) eV, IE(RhC) = 7.458(32) eV, IE(OsC) = 8.647(25) eV, IE(IrC) = 8.933(74) eV, and IE(PtC) = 9.397(32) eV. These experimentally derived IEs are further confirmed through quantum chemical calculations using coupled-cluster single double perturbative triple methods that are extrapolated to the complete basis set limit using a three-parameter mixed Gaussian/exponential extrapolation scheme and corrected for spin–orbit effects using a semiempirical method. The electronic structure and chemical bonding of these MC species are discussed in the context of these ionization energy measurements. The IEs of RuC, RhC, OsC, and IrC closely mirror the IEs of the corresponding transition metal atoms, suggesting that for these species, the (n + 1)s electrons of the transition metals are not significantly involved in chemical bonding.  more » « less
Award ID(s):
2305293
PAR ID:
10494033
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
American Institute of Physics
Date Published:
Journal Name:
The Journal of Chemical Physics
Volume:
160
Issue:
8
ISSN:
0021-9606
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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