scholarly journals The mechanism for catalytic hydrosilylation by bis(imino)pyridine iron olefin complexes supported by broken symmetry density functional theory

2017 ◽  
Vol 46 (37) ◽  
pp. 12507-12515 ◽  
Author(s):  
Yan Choi Lam ◽  
Robert J. Nielsen ◽  
William A. Goddard ◽  
Aswini K. Dash
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Broken Symmetry ◽  
Functional Theory ◽  
Catalytic Hydrosilylation

Broken-symmetry DFT supports a concerted migration of hydrogen from silane to olefin as the rate-determing step.

scholarly journals Use of Broken-Symmetry Density Functional Theory To Characterize the IspH Oxidized State: Implications for IspH Mechanism and Inhibition

2014 ◽  
Vol 10 (9) ◽  
pp. 3871-3884 ◽  
Author(s):  
Patrick G. Blachly ◽  
Gregory M. Sandala ◽  
Debra Ann Giammona ◽  
Tiqing Liu ◽  
Donald Bashford ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Broken Symmetry ◽  
Functional Theory

Subsystem density-functional theory for interacting open-shell systems: spin densities and magnetic exchange couplings

2020 ◽  
Vol 224 ◽  
pp. 201-226
Author(s):  
Anja Massolle ◽  
Johannes Neugebauer
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Open Shell ◽  
Broken Symmetry ◽  
Easy Access ◽  
Magnetic Exchange ◽  
Functional Theory ◽  
Spin Densities

Subsystem DFT allows easy access to spin densities for arbitrary broken-symmetry states of radical aggregates.

MAGNETIC COUPLING CONSTANTS AND SPIN DENSITY DISTRIBUTIONS FOR CYANO-BRIDGED Gd(III)-Fe(III) AND Gd(III)-Cr(III) COMPOUNDS: BROKEN-SYMMETRY AND DENSITY FUNCTIONAL THEORY CALCULATIONS

2005 ◽  
Vol 19 (15n17) ◽  
pp. 2538-2543 ◽  
Author(s):  
YI QUAN ZHANG ◽  
CHENG LIN LUO ◽  
ZHI YU
Keyword(s):  
Density Functional Theory ◽  
Spin Density ◽  
Spin Polarization ◽  
Density Functional ◽  
Population Analysis ◽  
Magnetic Coupling ◽  
Coupling Constants ◽  
Broken Symmetry ◽  
Functional Theory ◽  
Density Distributions

Magnetic coupling constants J for the complete structures of [ Gd(capro) 2( H 2 O )4 Cr(CN) 6]• H 2 O (capro represents caprolactam) (a) and trans-[ Fe(CN) 4(μ- CN )2 Gd ( H 2 O )4 (bpy) ]•4 H 2 O •1.5 bpy (b) have been calculated using hybrid density functional theory (DFT) B3LYP combined with a modified broken symmetry approach (BS). The calculated J value of -0.24 cm-1 for a is very close to the experimental -0.33 cm-1. They both show the antiferromagnetic interaction between Gd(III) and Cr(III) . For b, although the sign of the calculated J value of 4.24 cm-1 is different from that of the experimental -0.38 cm-1, the two values both show the weak magnetic coupling interaction between Gd(III) and Fe(III) . The spin density distributions are discussed on the basis of Mulliken population analysis. For complexes a and b, both transition metal ( Fe(III) or Cr(III) ) and rare earth Gd(III) display a spin polarization effect on the surrounding atoms, where a counteraction of the opposite polarization effects leads to a low spin density on the bridging ligand C1N1 . For the compounds Gd(III) - Cr(III) (a) and Gd(III) - Fe(III) (b) in the HS states, Cr(III) has stronger spin polarization influence on the bridging atoms than Fe(III) even causing the positive spin population on the bridging atom N1 .

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