Can Semiempirical Quantum Mechanics Be Used To Predict the Spin State of Transition Metal Complexes? An Application ofDe NovoPrediction

2002 ◽  
Vol 41 (1) ◽  
pp. 152-156 ◽  
Author(s):  
David M. Ball ◽  
Corneliu Buda ◽  
Aaron M. Gillespie ◽  
David P. White ◽  
Thomas R. Cundari
Keyword(s):  
Quantum Mechanics ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Spin State

Some critical issues in the application of quantum mechanics/molecular mechanics methods to the study of transition metal complexes

2003 ◽  
Vol 124 ◽  
pp. 429-441 ◽  
Author(s):  
David Balcells ◽  
Galí Drudis-Solé ◽  
Maria Besora ◽  
Nicole Dölker ◽  
Gregori Ujaque ◽  
...  
Keyword(s):  
Quantum Mechanics ◽  
Transition Metal ◽  
Metal Complexes ◽  
Molecular Mechanics ◽  
Transition Metal Complexes ◽  
Critical Issues

scholarly journals Should External Heavy-Atom Effects be Expected in Transition Metal Complexes?

2018 ◽  
Author(s):  
Justin Lomont ◽  
Son Nguyen ◽  
Charles Harris
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Spin State ◽  
Computational Study ◽  
Heavy Atom ◽  
Minimum Energy ◽  
Free Energy Barrier ◽  
Heavy Atom Effect ◽  
Atom Effect

Spin state changes frequently play a key role in the reactivity of transition metal complexes. The rates of spin-forbidden reactions are mediated both by the free energy barrier connecting reactants and products, as well as the strength of spin-orbit coupling (SOC) between the relevant electronic states. Since the 1950’s, there have been numerous demonstrations of external heavy-atom effects on organic molecules, in which a heavy atom, not chemically bonded to the molecule undergoing a change in spin state, perturbs the strength of SOC via an intermolecular effect. However, the potential role of external heavy atom effects on the rates of reactions involving transition metal complexes remains almost entirely unexplored. We report a computational investigation into the changes in SOC that occur along a bimolecular reaction coordinate when an incoming atom coordinates to the prototypical triplet reaction intermediate Fe(CO)4. The calculated changes in SOC are compared for molecules containing atoms ranging in atomic number from Z = 8 to Z = 53 approaching the Fe center (ZFe =26). No evidence for an external heavy atom effect was found, and the changes in SOC with the approach of each incoming group were similar in magnitude. In fact, when taking into account the different minimum energy crossing point geometries for the different incoming groups, the opposite of an external heavy atom effect trend is predicted for this reaction. The results of this computational study suggest that external heavy atom effects are unlikely to have a significant effect on the rates of spin-forbidden reactions for transition metal complexes. <br>

Revisiting the role of exact exchange in DFT spin-state energetics of transition metal complexes

2014 ◽  
Vol 16 (28) ◽  
pp. 14479-14488 ◽  
Author(s):  
Mariusz Radoń
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Spin State ◽  
Exact Exchange ◽  
Metal Ligand

Sensitivity of DFT spin-state energetics to exact exchange is rooted in the description of metal–ligand bonding.

scholarly journals Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics

2020 ◽  
Vol 22 (34) ◽  
pp. 19326-19341
Author(s):  
Aditya Nandy ◽  
Daniel B. K. Chu ◽  
Daniel R. Harper ◽  
Chenru Duan ◽  
Naveen Arunachalam ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Spin State ◽  
Large Scale ◽  
Transition Metal Complex ◽  
Large Data ◽  
Data Set ◽  
Large Data Set

The origin of distinct 3d vs. 4d transition metal complex sensitivity to exchange is explored over a large data set.

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