The Nonlocal Kernel in van der Waals Density Functionals as an Additive Correction: An Extensive Analysis with Special Emphasis on the B97M-V and ωB97M-V Approaches

Najibi, Asim; Goerigk, Lars

doi:10.1021/acs.jctc.8b00842

Cited by 246 publications

(337 citation statements)

References 149 publications

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“…[9,29] An octahedral ligand field splits the d manifold of the metal into t 2g and e g orbitals. While the results presented here were obtained with single reference Density Functional Theory (DFT), [33,34] the ωB97M-V functional [31] has proved very accurate both for main group [35,36] and transition metal [37] chemical energy differences. Spin crossover occurs in transition metal complexes when the energy required to pair spins to reach a low spin configuration is offset by the cost of maintaining a high spin configuration due to an increase in~O.…”

Section: Co] 2 +mentioning

confidence: 94%

Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes

2019

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Spin state switching on external stimuli is a phenomenon with wide applicability, ranging from molecular electronics to gas activation in nanoporous frameworks. Here, we model the spin crossover as a function of the hydrostatic pressure in octahedrally coordinated transition metal centers by applying a field of effective nuclear forces that compress the molecule towards its centroid. For spin crossover in first-row transition metals coordinated by hydrogen, nitrogen, and carbon monoxide, we find the pressure required for spin transition to be a function of the ligand position in the spectrochemical sequence. While pressures on the order of 1 GPa are required to flip spins in homogeneously ligated octahedral sites, we demonstrate a fivefold decrease in spin transition pressure for the archetypal strong field ligand carbon monoxide in octahedrally coordinated Fe 2 + in [Fe(II)(NH 3 ) 5 CO] 2 + .Pressure-induced spin-flips of transition metal sites involve changes in Coulomb energy, closed shell repulsions, covalent bonding energy and crystal field energy. [1,2] Using the computational Extreme-Pressure PCM (XP-PCM) protocol, [3][4][5] it has been shown that high pressures cause drastic electronic rearrangements, causing first row transition metals with electronic configurations d n (4 � n � 8) to favor low spin configurations at high pressures. [6] In a metal-organic framework (MOF) with exposed Fe(II) sites, a distinct step as a function of atmospheric pressure has been observed in the adsorption isotherm of carbon monoxide, for which a cooperative spin-transition mechanism involving interacting iron centers in the MOF on introduction of the strong-field ligand carbon monoxide has been proposed. [7] In general, the use of MOFs in the separation of industrially relevant gases like hydrogen, nitrogen and carbon monoxide holds a lot of promise, due to the large surface areas, the thermal stability and the adjustability of various parameters of the MOFs. [8] The smallest building block of spin crossover systems is often an octahedrally coordinated transition metal center with its 3d orbitals split by the ligand field environment. Spin-flip at high pressures can be attributed to the increase in splitting of the 3d levels at the metal site such that the potential energy required to maintain a high spin configuration surpasses the spin pairing energy. [9] Using effective nuclear forces scaled by their distances from the molecular centroid we here model spin crossover in octahedral metal-ligand complexes as a function of hydrostatic pressure. We find the pressure required for spin transition to be a function of ligand position in the spectrochemical sequence [10] and demonstrate that the spin transition pressure can be tuned by an adequate choice of the ligand field. Finer quantum chemical effects at play in the process involve a change in the covalent binding energy, Pauli repulsion, and charge transfer as a function of pressure, as demonstrated with an Energy Decomposition Analysis (EDA) [11] scheme.Any external force on...

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Section: Co] 2 +mentioning

confidence: 94%

Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes

2019

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“…In addition, the long-range parameter C was fixed as 0.0093, [60,62] which had been used for doublehybrid density functionals (DHDFs). [34,63,65,76] As suggested by Najibi and Goerigk, [78] the VV10NL correlation energy functional was added as an additive correction non-self-consistently.…”

Section: Methodsmentioning

confidence: 99%

“…The VV10NL correlation energy functional was based on electron density, and only a short‐range attenuation parameter needed to be fitted in general. The VV10NL correlation energy functional was widely used with different kinds of density functionals, and the density functionals including this nonlocal correlation energy functional showed very good performances on noncovalent interactions …”

Section: Introductionmentioning

confidence: 99%

“…With respect to the advantages of the dRPA75 method and the VV10NL correlation energy functional, the VV10NL correlation energy functional has been incorporated into the dRPA75 method as an additive correction in this work. The obtained method is dubbed as dRPA75‐NL, and the corresponding exchange‐correlation energy is given by

E_{XC}^{dRPA 75 ‐ NL} = ((), 0.75 E_{X}^{exact} + 0.25 E_{X}^{PBE} + E_{C}^{dRPA} + E_{C}^{NL}) @ PBE 0.75

…”

Section: Introductionmentioning

confidence: 99%

“…The VV10NL correlation energy functional was widely used with different kinds of density functionals, and the density functionals including this nonlocal correlation energy functional showed very good performances on noncovalent interactions. [34,[61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79] With respect to the advantages of the dRPA75 method and the VV10NL correlation energy functional, the VV10NL correlation energy functional has been incorporated into the dRPA75 method as an additive correction [78] in this work. The obtained method is dubbed as dRPA75-NL, and the corresponding exchange-correlation energy is given by…”

Section: Introductionmentioning

confidence: 99%

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Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions

Wang

2020

J Comput Chem

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We have added the nonlocal van der Waals correlation energy functional of Vydrov and Van Voorhis in 2010 (VV10NL) to the dual‐hybrid direct random phase approximation (dRPA75) and second‐order screened exchange (SOSEX75) for noncovalent interactions. The obtained methods are denoted as dRPA75‐NL and SOSEX75‐NL, and the corresponding short‐range attenuation parameters are fitted with the large aug‐cc‐pV5Z basis set against the S66 dataset. Therefore, the dRPA75‐NL method overcomes the error cancellation problem of the dRPA75 method with the relatively small aug‐cc‐pVTZ basis set for noncovalent interactions. Based on our benchmark computations, the dRPA75‐NL and SOSEX75‐NL methods perform very well on evaluating noncovalent interaction energies. Compared with the double‐hybrid density functionals (DHDFs) of DSD‐PBEP86‐NL and DOD‐PBEP86‐NL, the dRPA75‐NL and SOSEX75‐NL methods perform much better on charge transfer interactions. Furthermore, the SOSEX75‐NL method also gives insight into the development of computational methods for both closed‐shell and open‐shell noncovalent interactions. In summary, our computations demonstrate that even the full dRPA and SOSEX correlations still need additional dispersion corrections for noncovalent interactions.

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Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design

et al. 2022

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Computations and experiments leading to new chiral phosphoric acids (CPAs) for epoxide thionations are reported. Density functional theory calculations reveal the mechanism and origin of the enantioselectivity of such CPA‐catalyzed epoxide thionations. The calculated mechanistic information was used to design new efficient CPAs that were tested experimentally and found to be highly effective. Bulky ortho‐substituents on the 3,3′‐aryl groups of the CPA are important to restrict the position of the epoxide in the key transition states for the enantioselectivity‐determining step. Larger para‐substituents significantly improve the enantioselectivity of the reaction.

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The Nonlocal Kernel in van der Waals Density Functionals as an Additive Correction: An Extensive Analysis with Special Emphasis on the B97M-V and ωB97M-V Approaches

Cited by 246 publications

References 149 publications

Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes

Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes

Dual‐hybrid direct random phase approximation and second‐order screened exchange with nonlocal van der Waals correlations for noncovalent interactions

Chiral Phosphoric Acid Catalyzed Conversion of Epoxides into Thiiranes: Mechanism, Stereochemical Model, and New Catalyst Design

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