Theory of adiabatic Hexaamminecobalt-Self-Exchange
R. G. Endres, M. X. LaBute, D. L. Cox
Abstract
We have reexamined the thermally induced Co(NH3)62+/3+ [Co(II/III)] redox reaction using the first principles density-functional-theory method, semiclassical Marcus theory, and known charge transfer parameters. We confirm a previously suggested mechanism involving excited state (2Eg) of Co(II) which becomes lower than the ground state (4T1g) in the transition state region. This lowers the transition state barrier considerably by about 6.9 kcal/mol and leads to a spin-allowed and adiabatic electron exchange process. Our calculations are consistent with previous experimental results regarding the spin-excitation energy (3T1g) of Co(III), and the fact that an optical absorption peak (2Eg) of the Co(II) species could not be found experimentally. Our rate is of order 6 10-3 1/Ms and hence 2 orders of magnitude faster than determined previously by experiments.
Create a lesson
Related papers
Molecular Geometry Understanding Has Unintendedly Emerged in Frontier Large Language Models
Gregorii A. Semakin, Timofey V. Losev, Ilya V. Prolomov et al.
Truncated automatic sparse differentiation for machine learning interatomic potentials
Marcel F. Langer, Adrian Hill, Michele Ceriotti
Collective Ion Dynamics from Finite-Volume Fluctuations in Model Explicit-Solvent Electrolytes
Jeongmin Kim
FOSY: Segmental Backbone Assignment in Intrinsically Disordered Proteins
Dmitry M. Lesovoy, Tatiana Agback, Panagiota S. Georgoulia et al.
Efficient tensorized evaluation of permutation invariant polynomials for representing potential energy surfaces
Junhong Li, Kaisheng Song, Hua Guo et al.
DFT GGA based datasets for H2O potential energy surfaces, permanent moment and polarizability tensors
Anoop Ajaya Kumar Nair, Elvar Örn Jónsson