scholarly journals Benchmarking lithium amide versus amine bonding by charge density and energy decomposition analysis arguments

2018 ◽  
Vol 9 (12) ◽  
pp. 3111-3121 ◽  
Author(s):  
Felix Engelhardt ◽  
Christian Maaß ◽  
Diego M. Andrada ◽  
Regine Herbst-Irmer ◽  
Dietmar Stalke
Keyword(s):  
Quantum Theory ◽  
Dft Calculations ◽  
Charge Density ◽  
Decomposition Analysis ◽  
Atoms In Molecules ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Lithium Amide ◽  
Experimental Charge Density ◽  
Amide Versus

We investigated [{(Me2NCH2)2(C4H2N)}Li]2 (1) by means of experimental charge density calculations based on the quantum theory of atoms in molecules (QTAIM) and DFT calculations using energy decomposition analysis (EDA).

How electron-deficient Cp ligand facilitates Rh-catalyzed annulations with alkynes

2022 ◽  
Author(s):  
Han Gao ◽  
Lingfei Hu ◽  
Yanlei Hu ◽  
Xiangying Lv ◽  
Yanbo Wu ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Ligand Effects

The mechanism and origin of CpX ligand effects on Rh-catalyzed annulations with alkynes were investigated by using DFT calculations and the approach of energy decomposition analysis (EDA). The results reveal...

scholarly journals From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis

2021 ◽  
Vol 72 (1) ◽  
pp. 641-666
Author(s):  
Yuezhi Mao ◽  
Matthias Loipersberger ◽  
Paul R. Horn ◽  
Akshaya Das ◽  
Omar Demerdash ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Intermolecular Interaction ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Radical Cations ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Energy Decomposition ◽  
Functional Theory ◽  
Pauli Repulsion

Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. These energetic contributions are identified by performing DFT calculations with constraints that disable components of the interaction. This review describes the second-generation version of the absolutely localized molecular orbital EDA (ALMO-EDA-II). The effects of different physical contributions on changes in observables such as structure and vibrational frequencies upon complex formation are characterized via the adiabatic EDA. Example applications include red- versus blue-shifting hydrogen bonds; the bonding and frequency shifts of CO, N2, and BF bound to a [Ru(II)(NH3)5]2 + moiety; and the nature of the strongly bound complexes between pyridine and the benzene and naphthalene radical cations. Additionally, the use of ALMO-EDA-II to benchmark and guide the development of advanced force fields for molecular simulation is illustrated with the recent, very promising, MB-UCB potential.

scholarly journals A–X⋯σ Interactions—Halogen Bonds with σ-Electrons as the Lewis Base Centre

Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5175
Author(s):  
Sławomir J. Grabowski
Keyword(s):  
Quantum Theory ◽  
Molecular Hydrogen ◽  
Natural Bond Orbital ◽  
Decomposition Analysis ◽  
Lewis Base ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Halogen Bonds ◽  
Structural Database ◽  
Base Units

CCSD(T)/aug-cc-pVTZ//ωB97XD/aug-cc-pVTZ calculations were performed for halogen-bonded complexes. Here, the molecular hydrogen, cyclopropane, cyclobutane and cyclopentane act as Lewis base units that interact through the electrons of the H–H or C–C σ-bond. The FCCH, ClCCH, BrCCH and ICCH species, as well as the F2, Cl2, Br2 and I2 molecular halogens, act as Lewis acid units in these complexes, interacting through the σ-hole localised at the halogen centre. The Quantum Theory of Atoms in Molecules (QTAIM), the Natural Bond Orbital (NBO) and the Energy Decomposition Analysis (EDA) approaches were applied to analyse these aforementioned complexes. These complexes may be classified as linked by A–X···σ halogen bonds, where A = C, X (halogen). However, distinct properties of these halogen bonds are observed that depend partly on the kind of electron donor: dihydrogen, cyclopropane, or another cycloalkane. Examples of similar interactions that occur in crystals are presented; Cambridge Structural Database (CSD) searches were carried out to find species linked by the A–X···σ halogen bonds.

scholarly journals Looking at the big picture in activation strain model/energy decomposition analysis: the case of the ortho–para regioselectivity rule in Diels–Alder reactions

2020 ◽  
Vol 18 (6) ◽  
pp. 1104-1111 ◽  
Author(s):  
Nicolás Grimblat ◽  
Ariel M. Sarotti
Keyword(s):  
Dft Calculations ◽  
Decomposition Analysis ◽  
Diels Alder ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Big Picture ◽  
Strain Model

The regioselectivity of the DA reaction is predicted by the ortho–para rule which has been explained from FMO theory. Using DFT calculations and ASM/EDA, we found that the results vary depending the position where it is performed.

scholarly journals Probing radical–molecule interactions with a second generation energy decomposition analysis of DFT calculations using absolutely localized molecular orbitals

2020 ◽  
Vol 22 (23) ◽  
pp. 12867-12885
Author(s):  
Yuezhi Mao ◽  
Daniel S. Levine ◽  
Matthias Loipersberger ◽  
Paul R. Horn ◽  
Martin Head-Gordon
Keyword(s):  
Dft Calculations ◽  
Second Generation ◽  
Decomposition Analysis ◽  
Closed Shell ◽  
Energy Decomposition Analysis ◽  
Proper Treatment ◽  
Energy Decomposition ◽  
Localized Molecular Orbitals ◽  
Intermolecular Complexes ◽  
Molecule Interactions

Proper treatment of intermolecular complexes formed by radicals and closed-shell molecules in energy decomposition analysis of DFT calculations.

Characterization of fluorine-centred `F...O' σ-hole interactions in the solid state

2017 ◽  
Vol 73 (2) ◽  
pp. 140-152 ◽  
Author(s):  
Abhishek Sirohiwal ◽  
Venkatesha R. Hathwar ◽  
Dhananjay Dey ◽  
Roshni Regunathan ◽  
Deepak Chopra
Keyword(s):  
Solid State ◽  
Crystal Packing ◽  
Interaction Analysis ◽  
Decomposition Analysis ◽  
Atoms In Molecules ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Topological Features ◽  
Atomic Polarizability

In the current study, the crystal structure of 1-(3-nitrophenyl)-2,2,2-trifluoroethanone (A1) and (E)-4-((4-fluorophenyl) diazenyl)phenol (A2) has been analyzed for the characterization of the presence of a `unique' and `rare' intermolecular C(sp3/sp2)—F...O contact, which has been observed to play a significant role in the crystal packing. Theoretical charge-density calculations have been performed to study the nature and strength associated with the existence of this intermolecular F...O contact, wherein the F atom is attached to ansp3-hybridized C atom in the case of A1 and to ansp2hybridized carbon in the case of A2. The crystal packing of the former contains two `electronically different' Csp3—F...O contacts which are present across and in between the layers of molecules. In the latter case, it is characterized by the presence of a very `short' (2.708 Å) and `highly directional' (168° at ∠C4—F1...O1 and 174° at ∠C10—O1...F1) Csp2—F...O contact. According to the Cambridge Structural Database (CSD) study, it is a rare example in molecular crystals. Topological features of F...O contacts in the solid state were compared with the gas-phase models. The two-dimensional and three-dimensional static deformation density obtained from theoretical multipole modeling confirm the presence of a charge depleted region on the F atoms. Minimization of the electrostatic repulsion between like charges are observed through subtle arrangements in the electronic environment in two of the short intermolecular F...O contacts. These contacts were investigated using inputs from pair energy decomposition analysis, Bader's quantum theory of atoms in molecules (QTAIM), Hirshfeld surface analysis, delocalization index, reduced density gradient (RDG) plot, electrostatic potential surface and distributed atomic polarizability. The intermolecular energy decomposition (PIXEL) and RDG–NCI (non-covalent interaction) analysis of the F...O contacts establish the interaction to be dispersive in nature. The mutual polarization of an O atom by fluorine andviceversaprovides real physical insights into the role of atomic polarizability in interacting atoms in molecules in crystals.

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