Issue 1, 2006

Computational study of the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO

Abstract

Large basis CCSD(T) calculations are used to calculate the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO. The relative energy of the excited singlet state of Fe(CO)4 with respect to the ground triplet state is not known experimentally, and various lower levels of theory predict very different results. Upon extrapolating to the infinite basis set limit, and including corrections for core–core and core–valence correlation, scalar relativity, and multi-reference character of the wavefunction, the best CCSD(T) estimate for the spin-state splitting in iron tetracarbonyl is 2 kcal mol−1. Calculation of the dissociation energy of 1Fe(CO)4(L) into singlet fragments, taken together with known experimental behaviour of triplet Fe(CO)4, provides independent evidence for the fact that the spin-state splitting is smaller than 3 kcal mol−1. These calculations highlight some of the challenges involved in benchmark calculations on transition metal containing systems.

Graphical abstract: Computational study of the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO

Article information

Article type
Paper
Submitted
20 Sep 2005
Accepted
17 Oct 2005
First published
01 Nov 2005

Phys. Chem. Chem. Phys., 2006,8, 93-100

Computational study of the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO

J. Carreón-Macedo and J. N. Harvey, Phys. Chem. Chem. Phys., 2006, 8, 93 DOI: 10.1039/B513325D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements