Analytic Energy Gradients for Open-Shell Restricted-Hartree-Fock, Limited Multiconfiguration Scf, and Large Scale Configuration Interaction Wavefunctions.

1981 ◽  
pp. 161-174
Author(s):  
John D. Goddard
Keyword(s):  
Configuration Interaction ◽  
Large Scale ◽  
Open Shell ◽  
Hartree Fock

scholarly journals The Effect of Hartree-Fock Exchange on Scaling Relations and Reaction Energetics for C–H Activation Catalysts

2021 ◽  
Author(s):  
Vyshnavi Vennelakanti ◽  
Aditya Nandy ◽  
Heather Kulik
Keyword(s):  
Spin State ◽  
Density Functional ◽  
Large Scale ◽  
Predictive Power ◽  
Minimum Energy ◽  
Poor Performance ◽  
Closed Shell ◽  
Open Shell ◽  
Methanol Conversion ◽  
Hartree Fock

<p>High-throughput computational catalyst studies are typically carried out using density functional theory (DFT) with a single, approximate exchange-correlation functional. In open shell transition metal complexes (TMCs) that are promising for challenging reactions (e.g., C–H activation), the predictive power of DFT has been challenged, and properties are known to be strongly dependent on the admixture of Hartree-Fock (HF) exchange. We carry out a large-scale study of the effect of HF exchange on the predicted catalytic properties of over 1,200 mid-row (i.e., Cr, Mn, Fe, Co) 3<i>d </i>TMCs for direct methane-to-methanol conversion. Reaction energetic sensitivities across this set depend both on the catalytic rearrangement and ligand chemistry of the catalyst. These differences in sensitivities change both the absolute energetics predicted for a catalyst and its relative performance. Previous observations of the poor performance of global linear free energy relationships (LFERs) hold with both semi-local DFT widely employed in heterogeneous catalysis and hybrid DFT. Narrower metal/oxidation/spin-state specific LFERs perform better and are less sensitive to HF exchange than absolute reaction energetics, except in the case of some intermediate/high-spin states. Importantly, the interplay between spin-state dependent reaction energetics and exchange effects on spin-state ordering means that the choice of DFT functional strongly influences whether the minimum energy pathway is spin-conserved. Despite these caveats, LFERs involving catalysts that can be expected to have closed shell intermediates and low-spin ground states retain significant predictive power.</p>

scholarly journals The Effect of Hartree-Fock Exchange on Scaling Relations and Reaction Energetics for C–H Activation Catalysts

2021 ◽  
Author(s):  
Vyshnavi Vennelakanti ◽  
Aditya Nandy ◽  
Heather Kulik
Keyword(s):  
Spin State ◽  
Density Functional ◽  
Large Scale ◽  
Predictive Power ◽  
Minimum Energy ◽  
Poor Performance ◽  
Closed Shell ◽  
Open Shell ◽  
Methanol Conversion ◽  
Hartree Fock

<p>High-throughput computational catalyst studies are typically carried out using density functional theory (DFT) with a single, approximate exchange-correlation functional. In open shell transition metal complexes (TMCs) that are promising for challenging reactions (e.g., C–H activation), the predictive power of DFT has been challenged, and properties are known to be strongly dependent on the admixture of Hartree-Fock (HF) exchange. We carry out a large-scale study of the effect of HF exchange on the predicted catalytic properties of over 1,200 mid-row (i.e., Cr, Mn, Fe, Co) 3<i>d </i>TMCs for direct methane-to-methanol conversion. Reaction energetic sensitivities across this set depend both on the catalytic rearrangement and ligand chemistry of the catalyst. These differences in sensitivities change both the absolute energetics predicted for a catalyst and its relative performance. Previous observations of the poor performance of global linear free energy relationships (LFERs) hold with both semi-local DFT widely employed in heterogeneous catalysis and hybrid DFT. Narrower metal/oxidation/spin-state specific LFERs perform better and are less sensitive to HF exchange than absolute reaction energetics, except in the case of some intermediate/high-spin states. Importantly, the interplay between spin-state dependent reaction energetics and exchange effects on spin-state ordering means that the choice of DFT functional strongly influences whether the minimum energy pathway is spin-conserved. Despite these caveats, LFERs involving catalysts that can be expected to have closed shell intermediates and low-spin ground states retain significant predictive power.</p>

scholarly journals Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications

2021 ◽  
Author(s):  
P. Bernát Szabó ◽  
József Csóka ◽  
Mihály Kállay ◽  
Péter R. Nagy
Keyword(s):  
Large Scale ◽  
Open Shell ◽  
Linear Scaling

scholarly journals Large-scale ab initio configuration interaction calculations for light nuclei

2012 ◽  
Vol 403 ◽  
pp. 012019 ◽  
Author(s):  
Pieter Maris ◽  
H Metin Aktulga ◽  
Mark A Caprio ◽  
Ümit V Çatalyürek ◽  
Esmond G Ng ◽  
...  
Keyword(s):  
Ab Initio ◽  
Configuration Interaction ◽  
Large Scale ◽  
Light Nuclei ◽  
Configuration Interaction Calculations
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