scholarly journals Multiconfiguration Pair-Density Functional Theory for Transition Metal Silicide Bond Dissociation Energies, Bond Lengths, and State Orderings

Molecules ◽  
2021 ◽  
Vol 26 (10) ◽  
pp. 2881
Author(s):  
Meagan S. Oakley ◽  
Laura Gagliardi ◽  
Donald G. Truhlar
Keyword(s):  
Wave Function ◽  
Transition Metal ◽  
Density Functional ◽  
Bond Dissociation Energies ◽  
Complete Active Space ◽  
Active Space ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Pair Density ◽  
Self Consistent Field

Transition metal silicides are promising materials for improved electronic devices, and this motivates achieving a better understanding of transition metal bonds to silicon. Here we model the ground and excited state bond dissociations of VSi, NbSi, and TaSi using a complete active space (CAS) wave function and a separated-pair (SP) wave function combined with two post-self-consistent field techniques: complete active space with perturbation theory at second order and multiconfiguration pair-density functional theory. The SP approximation is a multiconfiguration self-consistent field method with a selection of configurations based on generalized valence bond theory without the perfect pairing approximation. For both CAS and SP, the active-space composition corresponds to the nominal correlated-participating-orbital scheme. The ground state and low-lying excited states are explored to predict the state ordering for each molecule, and potential energy curves are calculated for the ground state to compare to experiment. The experimental bond dissociation energies of the three diatomic molecules are predicted with eight on-top pair-density functionals with a typical error of 0.2 eV for a CAS wave function and a typical error of 0.3 eV for the SP approximation. We also provide a survey of the accuracy achieved by the SP and extended separated-pair approximations for a broader set of 25 transition metal–ligand bond dissociation energies.

THEORETICAL STUDIES ON BOND DISSOCIATION ENERGIES FOR SOME THIOL COMPOUNDS BY DENSITRY FUNCTIONAL THEORY AND CBS-Q METHOD

2008 ◽  
Vol 07 (05) ◽  
pp. 943-951 ◽  
Author(s):  
XIAO-HONG LI ◽  
ZHENG-XIN TANG ◽  
ABRAHAM F. JALBOUT ◽  
XIAN-ZHOU ZHANG ◽  
XIN-LU CHENG
Keyword(s):  
Density Functional ◽  
Computational Cost ◽  
Basis Set ◽  
Basis Sets ◽  
Q Method ◽  
Bond Dissociation Energies ◽  
Functional Theory ◽  
Thiol Compounds ◽  
Bond Dissociation ◽  
Dissociation Energies

Quantum chemical calculations are used to estimate the bond dissociation energies (BDEs) for 15 thiol compounds. These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86, PBE0) methods and the complete basis set (CBS-Q) method together with 6-311G** basis set. It is demonstrated that B3P86 and CBS-Q methods are accurate for computing the reliable BDEs for thiol compounds. In order to test whether the non-local BLYP method suggested by Fu et al.19 is general for our study and whether B3P86 method has a low basis set sensitivity, the BDEs for seven thiol compounds are also calculated using BLYP/6-31+G* and B3P86 method with 6-31+G*, 6-31+G**, and 6-311+G** basis sets for comparison. The obtained results are compared with the available experimental results. It is noted that B3P86 method is not sensitive to the basis set. Considering the inevitable computational cost of CBS-Q method and the reliability of the B3P86 calculations, B3P86 method with a moderate or a larger basis set may be more suitable to calculate the BDEs of the C–SH bond for thiol compounds.

Complete active space self‐consistent field and density functional study of FNO

1994 ◽  
Vol 100 (1) ◽  
pp. 459-463 ◽  
Author(s):  
Theodore S. Dibble ◽  
Joseph S. Francisco ◽  
Robert J. Deeth ◽  
Michael R. Hand ◽  
Ian H. Williams
Keyword(s):  
Density Functional ◽  
Functional Study ◽  
Density Functional Study ◽  
Complete Active Space ◽  
Active Space ◽  
Consistent Field ◽  
Self Consistent ◽  
Self Consistent Field

scholarly journals An Accurate and Efficient Method to Predict Y-NO Bond Homolysis Bond Dissociation Energies

2013 ◽  
Vol 2013 ◽  
pp. 1-10 ◽  
Author(s):  
Hong Zhi Li ◽  
Lin Li ◽  
Zi Yan Zhong ◽  
Yi Han ◽  
LiHong Hu ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Density Functional ◽  
Molecular Descriptors ◽  
Basis Set ◽  
Bond Dissociation Energies ◽  
Data Set ◽  
Test Set ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Bond Homolysis

The paper suggests a new method that combines the Kennard and Stone algorithm (Kenstone, KS), hierarchical clustering (HC), and ant colony optimization (ACO)-based extreme learning machine (ELM) (KS-HC/ACO-ELM) with the density functional theory (DFT) B3LYP/6-31G(d) method to improve the accuracy of DFT calculations for the Y-NO homolysis bond dissociation energies (BDE). In this method, Kenstone divides the whole data set into two parts, the training set and the test set; HC and ACO are used to perform the cluster analysis on molecular descriptors; correlation analysis is applied for selecting the most correlated molecular descriptors in the classes, and ELM is the nonlinear model for establishing the relationship between DFT calculations and homolysis BDE experimental values. The results show that the standard deviation of homolysis BDE in the molecular test set is reduced from 4.03 kcal mol−1calculated by the DFT B3LYP/6-31G(d) method to 0.30, 0.28, 0.29, and 0.32 kcal mol−1by the KS-ELM, KS-HC-ELM, and KS-ACO-ELM methods and the artificial neural network (ANN) combined with KS-HC, respectively. This method predicts accurate values with much higher efficiency when compared to the larger basis set DFT calculation and may also achieve similarly accurate calculation results for larger molecules.

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