Doubly hybrid density functionals that correctly describe both density and energy for atoms

Su, Neil Qiang; Zhu, Zhenqi; Xu, Xin

doi:10.1073/pnas.1713047115

Cited by 40 publications

(31 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The XYG3 type of doubly hybrid DFT The XYG3 61 types of doubly hybrid (xDH) density functional theory (DFT) have been shown to be remarkably accurate in describing noncovalent interactions of the main group elements. [62][63][64][65][66][67][68][69][70][71] Here the XYG3 functional is used to fully optimize all ion-π complexes. The 6-31+G (d) basis set is applied to benzene and the related arene π systems, while the 6-31G(d) basis set is applied to the derivatives of naphthalene, anthracene, and triphenylene.…”

Section: Computational Detailsmentioning

confidence: 99%

New Insights into the Ion-Specific Behaviors and Design Strategies for Ion–π Interactions

Liu

Chen

2021

CCS Chem

Self Cite

View full text Add to dashboard Cite

Ion-π interactions play a critical role in many important biological processes, such as gene expression, nicotine addiction, ion channel function, and so on, through recognizing specific ions by the receptors. However, widely used models, such as electrostatic potential and quadrupole moment, either treat ions as point charges or consider arenes only such that the key role of the information carried by ions is rarely discussed. Here, we shed light on the ion specificities in ion-π interactions by correlating binding energies to a new model, namely the orbital electrostatic energy (OEE), which describes the electrostatic properties of both ions and the π systems in detail via electron density distributions on orbitals. With this more detailed descriptor of electrostatics, new insights behind several important experimental and theoretical behaviors of ion-π interactions are revealed, which will provide a deeper understanding of molecular recognition and communication through ion-π interactions. On top of the OEE model, an ion-specific design strategy is proposed.

show abstract

Section: Computational Detailsmentioning

confidence: 99%

New Insights into the Ion-Specific Behaviors and Design Strategies for Ion–π Interactions

Liu

Chen

2021

CCS Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…Since atoms are the basic building block of molecules, a number of popular density functionals have been parametrized using ab initio data on noble gas atoms; these functionals have been used in turn as the starting point for the development of other functionals. A comparison of the results of density‐functional calculations to accurate ab initio data on atoms has, however, recently sparked controversy on the accuracy of a number of recently published, commonly used density functionals . This underlines that there is still room for improvement in DFT even for the relatively simple case of atomic studies.…”

Section: Introductionmentioning

confidence: 99%

A review on non‐relativistic, fully numerical electronic structure calculations on atoms and diatomic molecules

Lehtola

2019

Int J of Quantum Chemistry

102

View full text Add to dashboard Cite

The need for accurate calculations on atoms and diatomic molecules is motivated by the opportunities and challenges of such studies. The most commonly used approach for all-electron electronic structure calculations in general-the linear combination of atomic orbitals (LCAO) method-is discussed in combination with Gaussian, Slater a.k.a. exponential, and numerical radial functions. Even though LCAO calculations have major benefits, their shortcomings motivate the need for fully numerical approaches based on, for example, finite differences, finite elements, or the discrete variable representation, which are also briefly introduced. Applications of fully numerical approaches for general molecules are briefly reviewed, and their challenges are discussed. It is pointed out that the high level of symmetry present in atoms and diatomic molecules can be exploited to fashion more efficient fully numerical approaches for these special cases, after which it is possible to routinely perform allelectron Hartree-Fock and density functional calculations directly at the basis set limit on such systems. Applications of fully numerical approaches to calculations on atoms as well as diatomic molecules are reviewed. Finally, a summary and outlook is given.atomic calculations, density functional theory, diatomic calculations, fully numerical electronic structure theory, Hartree-Fock | INTRODUCTIONThanks to decades of development in approximate density functionals and numerical algorithms, density functional theory [1,2] (DFT) is now one of the cornerstones of computational chemistry and solid-state physics. [3][4][5] Since atoms are the basic building block of molecules, a number of popular density functionals [6][7][8][9][10] have been parametrized using ab initio data on noble gas atoms; these functionals have been used in turn as the starting point for the development of other functionals. A comparison of the results of density-functional calculations to accurate ab initio data on atoms has, however, recently sparked controversy on the accuracy of a number of recently published, commonly used density functionals. [11][12][13][14][15][16][17][18][19][20][21] This underlines that there is still room for improvement in DFT even for the relatively simple case of atomic studies.The development and characterization of new density functionals require the ability to perform accurate atomic calculations. Because atoms are the simplest chemical systems, atomic calculations may seem simple; however, they are in fact sometimes surprisingly challenging. For instance, a long-standing discrepancy between the theoretical and experimental electron affinity and ionization potential of gold has been resolved only very recently with high-level ab initio calculations. [22] Atomic calculations can also be used to formulate efficient starting guesses for molecular electronic structure calculations via either the atomic density [23,24] or the atomic potential as discussed in Ref. [25].

show abstract

“…21 In particular, the so-called double hybrid functionals, models including a fraction of HF exchange and a second-order Moller-Plesset (MP2) correlation contribution, present several advantages with respect to their Global Hybrids (GH) predecessors, including improved performances on larger domain of chemical applicability. [22][23][24][25] This is true, for instance, for thermochemistry, where some DHs rival in accuracy with some composite ab initio models. 26 Thanks to a balanced description of both covalent and non-covalent interactions, it is not rare that a DH model provides errors in the range of 1.0 to 1.5 kcal mol À1 on thermochemistry.…”

Section: Introductionmentioning

confidence: 99%

Pairing double hybrid functionals with a tailored basis set for an accurate thermochemistry of hydrocarbons

Brémond

Sancho‐García

et al. 2021

RSC Adv.

View full text Add to dashboard Cite

show abstract

Doubly hybrid density functionals that correctly describe both density and energy for atoms

Cited by 40 publications

References 64 publications

New Insights into the Ion-Specific Behaviors and Design Strategies for Ion–π Interactions

New Insights into the Ion-Specific Behaviors and Design Strategies for Ion–π Interactions

A review on non‐relativistic, fully numerical electronic structure calculations on atoms and diatomic molecules

Pairing double hybrid functionals with a tailored basis set for an accurate thermochemistry of hydrocarbons

Contact Info

Product

Resources

About