Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Videos

Fluctuation-dissipation theorem density-functional theory.

Filipp Furche1, Troy Van Voorhis

  • 1Institut für Physikalische Chemie, Universität Karlsruhe, Kaiserstrasse 12, Karlsruhe 76128, Germany.

The Journal of Chemical Physics
|June 11, 2005
PubMed
Summary
This summary is machine-generated.

Related Concept Videos

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

How to Use Quantum Computers for Biomolecular Free Energies.

Journal of chemical theory and computation·2026
Same author

Thermal and vibronic effects on the absorption spectra of II-VI quantum dots: Atomistic origins of the Urbach tail.

The Journal of chemical physics·2026
Same author

Unexpected dispersion-stabilized tris(terphenylthiolate) complexes, Ln(SAr <sup><i>i</i>Pr6</sup>)<sub>3</sub>, arising from two-electron reduction by Ln(SAr <sup><i>i</i>Pr6</sup>)<sub>2</sub> [Ar <sup><i>i</i>Pr6</sup> = C<sub>6</sub>H<sub>3</sub>-2,6-(C<sub>6</sub>H<sub>2</sub>-2,6,4- <sup><i>i</i></sup> Pr<sub>3</sub>)<sub>2</sub>].

Chemical science·2026
Same author

Isolable Cuprocenes: Bis(tri-<i>tert</i>-butylcyclopentadienyl) Complexes of Copper.

Journal of the American Chemical Society·2026
Same author

C T symmetry in nonlinear time-dependent electronic structure theories.

The Journal of chemical physics·2025
Same author

Band Alignment in Core-Shell Nanocrystals by Estimating Wave Function Tunneling Probabilities.

Nano letters·2025
Same journal

Revisiting crossed-correlated baths in open quantum systems simulated by HEOM or T-TEDOPA.

The Journal of chemical physics·2026
Same journal

Vesicle size and membrane composition control monomer transfer pathways in multicomponent lipid vesicles.

The Journal of chemical physics·2026
Same journal

Polaron-mediated exciton dynamics of P(NDI2OD-T2) unveiled by transient absorption spectroscopy under electrochemical conditions.

The Journal of chemical physics·2026
Same journal

Green-Kubo relation in a mesoscale odd fluid model.

The Journal of chemical physics·2026
Same journal

Nitrogenation of microscopic MoS2 surfaces by oxidation scanning probe lithography.

The Journal of chemical physics·2026
Same journal

Molecular structure, binding, and disorder in TDBC-Ag plexcitonic assemblies.

The Journal of chemical physics·2026
See all related articles

The fluctuation-dissipation theorem in density-functional theory (DFT) offers a new way to calculate correlation energy, naturally including dispersion interactions. However, beyond the random-phase approximation, certain approximations lead to unphysical results, though hybrid functionals show promise.

Area of Science:

  • Quantum Chemistry
  • Computational Physics
  • Materials Science

Background:

  • Conventional Kohn-Sham density-functional theory (DFT) faces challenges in accurately describing correlation energy and dispersion interactions.
  • The fluctuation-dissipation theorem (FDT) provides an exact expression for ground-state correlation energy using the density response function.
  • Combining FDT with time-dependent DFT (TDDFT) yields new density functionals incorporating approximations to the exchange-correlation kernel (fxc).

Purpose of the Study:

  • To present the first benchmark results for molecules using FDT-DFT beyond the random-phase approximation (RPA).
  • To investigate the performance of FDT-DFT with non-zero exchange-correlation kernels (fxc != 0).
  • To assess the accuracy of dispersion interactions using FDT-DFT with different functional approximations.

Related Experiment Videos

Main Methods:

  • Application of the fluctuation-dissipation theorem within density-functional theory (FDT-DFT).
  • Utilizing time-dependent density-functional theory (TDDFT) to construct new density functionals.
  • Benchmarking calculations on molecular systems using FDT-DFT beyond the random-phase approximation (RPA).
  • Employing adiabatic local-density approximation and semilocal functionals for the exchange-correlation kernel (fxc).

Main Results:

  • FDT-DFT beyond RPA, with fxc != 0, is explored for the first time on molecular systems.
  • Adiabatic local-density approximation and semilocal kernels exhibit an 'ultraviolet catastrophe,' causing pair density divergence at short interparticle distances.
  • Hybrid functionals within FDT-DFT accurately describe dispersion interactions, as demonstrated for He2 and HeNe dimers.

Conclusions:

  • FDT-DFT offers a promising route to improve correlation energy calculations and naturally include dispersion.
  • Approximations to the exchange-correlation kernel (fxc) beyond RPA require careful consideration to avoid unphysical divergences.
  • Hybrid functionals show potential for accurate dispersion treatment within the FDT-DFT framework, guiding future research.