scholarly journals Defining the contributions of permanent electrostatics, Pauli repulsion, and dispersion in density functional theory calculations of intermolecular interaction energies

2016 ◽  
Vol 144 (11) ◽  
pp. 114107 ◽  
Author(s):  
Paul R. Horn ◽  
Yuezhi Mao ◽  
Martin Head-Gordon
Keyword(s):  
Density Functional Theory ◽  
Intermolecular Interaction ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Interaction Energies ◽  
Functional Theory ◽  
Pauli Repulsion

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.

On the Nature of Alkali Ion−Water Interactions: Insights from Many-Body Representations and Density Functional Theory. II.

2020 ◽  
Author(s):  
Colin K. Egan ◽  
Brandon B. Bizzarro ◽  
Marc Riera ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Kinetic Energy Density ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory ◽  
Hartree Fock ◽  
Close Range ◽  
Pauli Repulsion ◽  
Alkali Ion

<div> <div> <div> <p>Interaction energies of alkali ion−water dimers, M<sup>+</sup>(H<sub>2</sub>O), and trimers, M<sup>+</sup>(H<sub>2</sub>O)<sub>2</sub>, with M = Li, Na, K, Rb, Cs, are investigated using various many-body potential energy functions, and exchange correlation functionals selected across the hierarchy of density functional theory approximations. Analysis of interaction energy decompositions indicates that close range interactions such as Pauli repulsion, charge transfer, and charge penetration must be captured in order to reproduce accurate interaction energies. In particular, it is found that simple classical polarizable models must be supplemented with dedicated terms which account for these close range interactions in order to achieve chemical accuracy across configuration space. It is also found that the XC functionals mostly differ from each other in their Pauli repulsion + Dispersion energies, and hence benefit from the inclusion of nonlocal terms such as Hartree-Fock exchange and dependence on the electronic kinetic energy density in order to reproduce the interactions that contribute to this term, namely Pauli repulsion and (intermediate-range) dispersion. As a continuation of the analysis performed in J. Chem. Theory Comput. 2019, 15, 2983, we make comparisons between findings for alkali ion−water interactions with those for halide−water interactions. </p> </div> </div> </div>

On the Nature of Alkali Ion−Water Interactions: Insights from Many-Body Representations and Density Functional Theory. II.

2020 ◽  
Author(s):  
Colin K. Egan ◽  
Brandon B. Bizzarro ◽  
Marc Riera ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Kinetic Energy Density ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory ◽  
Hartree Fock ◽  
Close Range ◽  
Pauli Repulsion ◽  
Alkali Ion

<div> <div> <div> <p>Interaction energies of alkali ion−water dimers, M<sup>+</sup>(H<sub>2</sub>O), and trimers, M<sup>+</sup>(H<sub>2</sub>O)<sub>2</sub>, with M = Li, Na, K, Rb, Cs, are investigated using various many-body potential energy functions, and exchange correlation functionals selected across the hierarchy of density functional theory approximations. Analysis of interaction energy decompositions indicates that close range interactions such as Pauli repulsion, charge transfer, and charge penetration must be captured in order to reproduce accurate interaction energies. In particular, it is found that simple classical polarizable models must be supplemented with dedicated terms which account for these close range interactions in order to achieve chemical accuracy across configuration space. It is also found that the XC functionals mostly differ from each other in their Pauli repulsion + Dispersion energies, and hence benefit from the inclusion of nonlocal terms such as Hartree-Fock exchange and dependence on the electronic kinetic energy density in order to reproduce the interactions that contribute to this term, namely Pauli repulsion and (intermediate-range) dispersion. As a continuation of the analysis performed in J. Chem. Theory Comput. 2019, 15, 2983, we make comparisons between findings for alkali ion−water interactions with those for halide−water interactions. </p> </div> </div> </div>

scholarly journals Interaction of water with (silico)aluminophosphate zeotypes: a comparative investigation using dispersion-corrected DFT

2016 ◽  
Vol 18 (23) ◽  
pp. 15738-15750 ◽  
Author(s):  
Michael Fischer
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Structural Changes ◽  
Water Adsorption ◽  
Density Functional Theory Calculations ◽  
Comparative Investigation ◽  
Interaction Energies ◽  
Functional Theory ◽  
Adsorption Of Water

The adsorption of water in six structurally different aluminophosphates and their silicoaluminophosphate analogues is investigated using dispersion-corrected density-functional theory calculations. In addition to predicting the interaction energies, the structural changes of the materials upon water adsorption are assessed.

On the Nature of Halide-Water Interactions: Insights from Many-Body Representations and Density Functional Theory

2019 ◽  
Author(s):  
Brandon B. Bizzarro ◽  
Colin K. Egan ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Molecular Orbital ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Orbital Energy ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory

<div> <div> <div> <p>Interaction energies of halide-water dimers, X<sup>-</sup>(H<sub>2</sub>O), and trimers, X<sup>-</sup>(H<sub>2</sub>O)<sub>2</sub>, with X = F, Cl, Br, and I, are investigated using various many-body models and exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. Analysis of the results obtained with the many-body models demonstrates the need to capture important short-range interactions in the regime of large inter-molecular orbital overlap, such as charge transfer and charge penetration. Failure to reproduce these effects can lead to large deviations relative to reference data calculated at the coupled cluster level of theory. Decompositions of interaction energies carried out with the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method demonstrate that permanent and inductive electrostatic energies are accurately reproduced by all classes of XC functionals (from generalized gradient corrected (GGA) to hybrid and range-separated functionals), while significant variance is found for charge transfer energies predicted by different XC functionals. Since GGA and hybrid XC functionals predict the most and least attractive charge transfer energies, respectively, the large variance is likely due to the delocalization error. In this scenario, the hybrid XC functionals are then expected to provide the most accurate charge transfer energies. The sum of Pauli repulsion and dispersion energies are the most varied among the XC functionals, but it is found that a correspondence between the interaction energy and the ALMO EDA total frozen energy may be used to determine accurate estimates for these contributions. </p> </div> </div> </div>

Is a Non-Transition Element Nitride Ferromagnet Ever Achievable? Indication of the N-N Pairing Instability

2006 ◽  
Vol 71 (11-12) ◽  
pp. 1525-1531 ◽  
Author(s):  
Wojciech Grochala
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Transition Element ◽  
Density Functional Theory Calculations ◽  
Functional Theory

The enthalpy of four polymorphs of CaN has been scrutinized at 0 and 100 GPa using density functional theory calculations. It is shown that structures of diamagnetic calcium diazenide (Ca2N2) are preferred over the cubic ferromagnetic polymorph (CaN) postulated before, both at 0 and 100 GPa.

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