Double-hybrid density-functional theory applied to molecular crystals.

@article{Sharkas2014DoublehybridDT,
  title={Double-hybrid density-functional theory applied to molecular crystals.},
  author={Kamal Sharkas and Julien Toulouse and Lorenzo Maschio and Bartolomeo Civalleri},
  journal={The Journal of chemical physics},
  year={2014},
  volume={141 4},
  pages={
          044105
        }
}
We test the performance of a number of two- and one-parameter double-hybrid approximations, combining semilocal exchange-correlation density functionals with periodic local second-order Møller-Plesset (LMP2) perturbation theory, for calculating lattice energies of a set of molecular crystals: urea, formamide, ammonia, and carbon dioxide. All double-hybrid methods perform better on average than the corresponding Kohn-Sham calculations with the same functionals, but generally not better than… 
25 Citations

Figures and Tables from this paper

Range-separated double-hybrid density-functional theory applied to periodic systems.

These range-separated double hybrids provide a good accuracy for binding energies using basis sets of moderate sizes such as cc-pVDZ and aug-cc-pVBZ and a reasonable choice for solids.

Range-Separated Double-Hybrid Functional from Nonempirical Constraints.

Tests show that RSX-QIDH is competitive with the more empirical ωB97X-2 double hybrid and outperforms the parent LC-PBE long-range corrected hybrid, thus underlining the important role of the nonlocal perturbative correlation.

On the performance of time-dependent double-hybrid density functionals for description of absorption and emission spectra of heteroaromatic compounds

  • M. Alipour
  • Chemistry
    Theoretical Chemistry Accounts
  • 2016
Theoretical chemistry provides a panel of powerful tools to investigate the geometries and electronic properties of excited states. However, it is necessary to benchmark the accuracy of existing

Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method.

An orbital-optimized double-hybrid (DH) scheme using the optimized-effective-potential (OEP) method that improves the accuracy of electron affinities and restores the meaning of the LUMO orbital energy as being connected to a neutral excitation energy.

State-of-the-Art Calculations of Sublimation Enthalpies for Selected Molecular Crystals and Their Computational Uncertainty.

Temperature-dependent sublimation enthalpies for a set of selected 22 molecular crystals in their low-temperature phases are calculated by a computational methodology developed and validated by comparison to critically evaluated literature experimental data.

Designing a paradigm for parameter-free double-hybrid density functionals through the adiabatic connection path

  • M. Alipour
  • Chemistry
    Theoretical Chemistry Accounts
  • 2015
It is now well established that the double-hybrid (DH) approximations belong to the most accurate methodologies for various properties and electronic structure calculations in the framework of

Determining the cohesive energy of coronene by dispersion-corrected DFT methods: periodic boundary conditions vs. molecular pairs.

The nature and importance of the binding forces in every molecular pair tackled are revealed and revised estimates of the effects of two- and three-body terms are provided, leading to accurate results in close agreement with experimental (sublimation enthalpies) reference values.

Assessment of Different Quantum Mechanical Methods for the Prediction of Structure and Cohesive Energy of Molecular Crystals.

A comparative assessment of the accuracy of different quantum mechanical methods for evaluating the structure and the cohesive energy of molecular crystals is presented and the B3LYP-D* method combined with a TZP basis set gives the best results.

CCSD(T)/CBS fragment-based calculations of lattice energy of molecular crystals.

Locally and explicitly correlated methods are found to be computationally effective and reliable methods enabling the application of fragment-based methods for larger systems.

References

SHOWING 1-10 OF 122 REFERENCES

Double-hybrid density-functional theory made rigorous.

This work provides a rigorous derivation of a class of double-hybrid approximations, combining Hartree-Fock exchange and second-order Møller-Plesset correlation with a semilocal exchange-correlation density functional, showing that these methods are not only empirically close to an optimum for general chemical applications but are also theoretically supported.

Towards chemical accuracy for the thermodynamics of large molecules: new hybrid density functionals including non-local correlation effects.

The big improvement compared to common density functionals is further demonstrated by the reduction of the maximum and minimum errors (outliers) and by much smaller errors for complicated molecular systems.

The embedded many-body expansion for energetics of molecular crystals.

It is shown that accurate results can be obtained from a monomer-based many-body expansion truncated at the two-body level, with the monomer and dimer calculations suitably embedded in a model of the crystalline environment.

Periodic density functional theory calculations for 3-dimensional polyacetylene with empirical dispersion terms.

In this report periodic B3LYP density functional theory calculations for three-dimensional (3D) trans-polyacetylene (t-PA) fibers, the out-of-phase P2(1)/n structure turns out to be a transition state for the interchain relative translational motion, which lies about 0.35 kcal mol(-1) above the two symmetrically located in- phase P2 (1)/a minima.

Density functional theory and molecular clusters

DFT interaction energy exhibits the same basis set extension dependence as the Hartree‐Fock (HF) interaction energy, so the Boys‐Bernardi function counterpoise procedure should be employed for elimination of the DFT basis set superposition error.

Periodic local Møller-Plesset second order perturbation theory method applied to molecular crystals: study of solid NH3 and CO2 using extended basis sets.

The present paper calculated the equilibrium geometry, formation energy, and bulk modulus of two molecular bulk crystals, NH(3) and CO(2), at the periodic post-Hartree-Fock correlated level using the periodic local Møller-Plesset second order perturbation theory (LMP2), implemented in the CRYSCOR program.

Ab initio study of van der Waals and hydrogen-bonded molecular crystals with a periodic local-MP2 method

We have studied ab initio the cohesive energy of a set of six molecular crystals with CRYSCOR, a new program implementing a periodic local second-order Moller–Plesset perturbation theory (LMP2)

Local MP2 with Density Fitting for Periodic Systems: A Parallel Implementation.

  • L. Maschio
  • Computer Science
    Journal of chemical theory and computation
  • 2011
A parallel implementation is presented for the evaluation of local second-order Møller-Plesset perturbation theory (LMP2) energies in periodic, nonconducting crystalline systems with a

Intermolecular interaction energies in molecular crystals: comparison and agreement of localized Møller-Plesset 2, dispersion-corrected density functional, and classical empirical two-body calculations.

The study confirms that pure DFT shows serious deficiencies in properly handling molecular crystals in which the dispersive contribution is large, and shows that both DFT-D and PIXEL approaches are robust predictive tools for studying molecular crystals.
...