Mapping the d-d excited-state manifolds of transition metal beta-diiminato-imido complexes. Comparison of density functional theory and CASPT2 energetics

The Journal of Physical Chemistry. a
Abhik GhoshBjörn O Roos

Abstract

Trigonal-planar, middle transition metal diiminato-imido complexes do not exhibit high-spin states, as might be naively expected on the basis of their low coordination numbers. Instead, the known Fe(III), Co(III), and Ni(III) complexes exhibit S = 3/2, S = 0, and S = 1/2 ground states, respectively. Kohn-Sham DFT calculations have provided a basic molecular orbital picture of these compounds as well as a qualitative rationale for the observed spin states. Reported herein are ab initio multiconfiguration second-order perturbation theory (CASPT2) calculations, which provide a relatively detailed picture of the d-d excited-state manifolds of these complexes. Thus, for a C(2v) Fe(III)(diiminato)(NPh) model complex, two near-degenerate states ((4)B(2) and (4)B(1)) compete as contenders for the ground state. Moreover, the high-spin sextet, two additional quartets and even a low-spin doublet all occur at <0.5 eV, relative to the ground state. For the Co(III) system, although CASPT2 reproduces an S = 0 ground state, as observed experimentally for a related complex, the calculations also predict two exceedingly low-energy triplet states; there are, however, no other particularly low-energy d-d excited states. In contrast to the Fe(III) ...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Dec 19, 2002·Journal of the American Chemical Society·David M JenkinsJonas C Peters
Apr 11, 2003·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Abhik GhoshPeter R Taylor
Apr 15, 2004·Journal of the American Chemical Society·Xuliang DaiTimothy H Warren
Dec 17, 2004·Journal of the American Chemical Society·Xile Hu, Karsten Meyer
Feb 5, 2005·Angewandte Chemie·Daniel T ShayKlaus H Theopold
Jun 22, 2005·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Latévi Max Lawson DakuMark Earl Casida
Aug 11, 2005·Journal of the American Chemical Society·Elzbieta KogutTimothy H Warren
Jul 13, 2006·The Journal of Physical Chemistry. a·André R GroenhofKoop Lammertsma
Jul 13, 2006·The Journal of Physical Chemistry. a·Björn O RoosPer-Olof Widmark
Jul 15, 2006·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Abhik Ghosh
Sep 23, 2006·Angewandte Chemie·Nathan A EckertPatrick L Holland
Jan 26, 2007·The Journal of Physical Chemistry. B·Nikki Strickland, Jeremy N Harvey
Feb 10, 2007·Journal of the American Chemical Society·Ryan E CowleyJeremy M Smith
Oct 16, 2007·The Journal of Physical Chemistry. B·Jeanet Conradie, Abhik Ghosh
Mar 1, 2007·Journal of Chemical Theory and Computation·Espen TangenAbhik Ghosh

❮ Previous
Next ❯

Citations

Jun 28, 2013·Inorganic Chemistry·Olayinka A Olatunji-Ojo, Thomas R Cundari
Nov 20, 2009·Physical Chemistry Chemical Physics : PCCP·Christopher J Cramer, Donald G Truhlar
Mar 22, 2013·The Journal of Chemical Physics·Werner GyőrffyHans-Joachim Werner
Jul 24, 2015·The Journal of Chemical Physics·Efthymios I Ioannidis, Heather J Kulik
Mar 22, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Tibor András RokobLubomír Rulíšek
Jun 6, 2009·Journal of Computational Chemistry·Francesco AquilanteRoland Lindh
Dec 10, 2009·Inorganic Chemistry·Jeanet Conradie, Abhik Ghosh
Dec 8, 2010·Journal of Inorganic Biochemistry·Marrigje M ConradieAbhik Ghosh
Nov 12, 2013·Journal of Chemical Theory and Computation·Yuanyuan Sun, Hui Chen

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.