Charge Decomposition Analysis (CDA)

2016 ◽  
Author(s):  
Vladimir I. Minkin
Keyword(s):  
Decomposition Analysis ◽  
Charge Decomposition Analysis

scholarly journals The transition metal to ligand bonding nature: A quantum chemical study of π-allyl-ruthenacycle molecule

2018 ◽  
Vol 58 (3) ◽  
Author(s):  
Aušra Vektarienė
Keyword(s):  
Transition Metal ◽  
Physical Properties ◽  
Density Functional ◽  
Quantum Chemical Study ◽  
Decomposition Analysis ◽  
Computational Procedure ◽  
Chemical Study ◽  
Hartree Fock ◽  
Charge Decomposition Analysis ◽  
The Density Functional Theory

Understanding of the transition metal (TM) to ligand (L) bonding nature is important for characterization of experimental observations. One of the methods to explain the TM to L interactions is the Dewar–Chatt–Duncanson (DCD) model. However, in most applications the validity of the DCD model is based on assumptions in order to explain trends in vibrational spectroscopy or other physical properties of TM complexes. In this paper the computational methodology for treatment of the π-allyl-ruthenacycle complex based on the density functional theory, restricted Hartree–Fock method, natural bond orbital and charge decomposition analysis is reported. It is shown how the DCD model emerges from the presented calculation scheme and how it relates with the physical properties and stability of this complex. It is important to note that in this work the determination of the DCD model operation is based on the defined computational procedure, not postulated beforehand. The calculated geometry parameters, vibrational frequencies and electron density arrangement for the π-allyl-ruthenacycle complex are in good agreement with the experiment and support the DCD model.

Enhanced π-back-donation resulting in the trans labilization of a pyridine ligand in an N-heterocyclic carbene (NHC) PdII precatalyst: a case study

2019 ◽  
Vol 75 (7) ◽  
pp. 941-950
Author(s):  
Hande Karabıyık ◽  
Beyhan Yiğit ◽  
Murat Yiğit ◽  
İsmail Özdemir ◽  
Hasan Karabıyık
Keyword(s):  
Structural Characteristics ◽  
Decomposition Analysis ◽  
Pyridine Ligand ◽  
Charge Decomposition Analysis ◽  
Ir And Nmr Spectroscopy ◽  
Type Hydrogen Bond ◽  
Structural Database ◽  
The Individual ◽  
Back Donation

The molecular structure of the benzimidazol-2-ylidene–PdCl2–pyridine-type PEPPSI (pyridine-enhanced precatalyst, preparation, stabilization and initiation) complex {1,3-bis[2-(diisopropylamino)ethyl]benzimidazol-2-ylidene-κC 2}dichlorido(pyridine-κN)palladium(II), [PdCl2(C5H5N)(C23H40N4)], has been characterized by elemental analysis, IR and NMR spectroscopy, and natural bond orbital (NBO) and charge decomposition analysis (CDA). Cambridge Structural Database (CSD) searches were used to understand the structural characteristics of the PEPPSI complexes in comparison with the usual N-heterocyclic carbene (NHC) complexes. The presence of weak C—H...Cl-type hydrogen-bond and π–π stacking interactions between benzene rings were verified using NCI plots and Hirshfeld surface analysis. The preferred method in the CDA of PEPPSI complexes is to separate their geometries into only two fragments, i.e. the bulky NHC ligand and the remaining fragment. In this study, the geometry of the PEPPSI complex is separated into five fragments, namely benzimidazol-2-ylidene (Bimy), two chlorides, pyridine (Py) and the PdII ion. Thus, the individual roles of the Pd atom and the Py ligand in the donation and back-donation mechanisms have been clearly revealed. The NHC ligand in the PEPPSI complex in this study acts as a strong σ-donor with a considerable amount of π-back-donation from Pd to Ccarbene. The electron-poor character of PdII is supported by π-back-donation from the Pd centre and the weakness of the Pd—N(Py) bond. According to CSD searches, Bimy ligands in PEPPSI complexes have a stronger σ-donating ability than imidazol-2-ylidene ligands in PEPPSI complexes.

Donor-driven conformational flexibility in a real-life catalytic dicopper(ii) peroxo complex

2016 ◽  
Vol 18 (9) ◽  
pp. 6430-6440 ◽  
Author(s):  
A. Hoffmann ◽  
S. Herres-Pawlis
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Real Life ◽  
Decomposition Analysis ◽  
Conformational Flexibility ◽  
Peroxo Complex ◽  
Dft Studies ◽  
Functional Theory ◽  
Charge Decomposition Analysis ◽  
Second Order Perturbation Theory

The conformers of the real-life tyrosinase model [Cu2O2{HC(3-tBuPz)2(Py)}2]2+which displays catalytic hydroxylation reactivity were investigated by density functional theory (DFT) studies including second-order perturbation theory and charge decomposition analysis (CDA).

scholarly journals DFT-D4 Insight into the Inclusion of Amphetamine and Methamphetamine in Cucurbit[7]uril: Energetic, Structural and Biosensing Properties

Molecules ◽  
2021 ◽  
Vol 26 (24) ◽  
pp. 7479
Author(s):  
Abdelkarim Litim ◽  
Youghourta Belhocine ◽  
Tahar Benlecheb ◽  
Monira Galal Ghoniem ◽  
Zoubir Kabouche ◽  
...  
Keyword(s):  
Density Functional ◽  
Hydrophobic Interactions ◽  
Decomposition Analysis ◽  
Atomic Charge ◽  
Density Functional Theory Calculations ◽  
Frontier Molecular Orbital ◽  
Recognition Mechanism ◽  
Water Solvent ◽  
Charge Decomposition Analysis ◽  
Molecular Orbital Analysis

The host–guest interactions of cucurbit[7]uril (CB[7]) as host and amphetamine (AMP), methamphetamine (MET) and their enantiomeric forms (S-form and R-form) as guests were computationally investigated using density functional theory calculations with the recent D4 atomic-charge dependent dispersion corrections. The analysis of energetic, structural and electronic properties with the aid of frontier molecular orbital analysis, charge decomposition analysis (CDA), extended charge decomposition analysis (ECDA) and independent gradient model (IGM) approach allowed to characterize the host–guest interactions in the studied systems. Energetic results indicate the formation of stable non-covalent complexes where R-AMP@CB[7] and S-AMP@CB[7] are more stable thermodynamically than R-MET@CB[7] and S-MET@CB[7] in gas phase while the reverse is true in water solvent. Based on structural analysis, a recognition mechanism is proposed, which suggests that the synergistic effect of van der Waals forces, ion–dipole interactions, intermolecular charge transfer interactions and intermolecular hydrogen bonding is responsible for the stabilization of the complexes. The geometries of the complexes obtained theoretically are in good agreement with the X-ray experimental structures and indicate that the phenyl ring of amphetamine and methamphetamine is deeply buried into the cavity of CB[7] through hydrophobic interactions while the ammonium group remains outside the cavity to establish hydrogen bonds with the portal oxygen atoms of CB[7].

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