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Exchange-correlation energy from pairing matrix fluctuation and the particle-particle random phase approximation.

Publication ,  Journal Article
van Aggelen, H; Yang, Y; Yang, W
Published in: The Journal of chemical physics
May 2014

Despite their unmatched success for many applications, commonly used local, semi-local, and hybrid density functionals still face challenges when it comes to describing long-range interactions, static correlation, and electron delocalization. Density functionals of both the occupied and virtual orbitals are able to address these problems. The particle-hole (ph-) Random Phase Approximation (RPA), a functional of occupied and virtual orbitals, has recently known a revival within the density functional theory community. Following up on an idea introduced in our recent communication [H. van Aggelen, Y. Yang, and W. Yang, Phys. Rev. A 88, 030501 (2013)], we formulate more general adiabatic connections for the correlation energy in terms of pairing matrix fluctuations described by the particle-particle (pp-) propagator. With numerical examples of the pp-RPA, the lowest-order approximation to the pp-propagator, we illustrate the potential of density functional approximations based on pairing matrix fluctuations. The pp-RPA is size-extensive, self-interaction free, fully anti-symmetric, describes the strong static correlation limit in H2, and eliminates delocalization errors in H2(+) and other single-bond systems. It gives surprisingly good non-bonded interaction energies--competitive with the ph-RPA--with the correct R(-6) asymptotic decay as a function of the separation R, which we argue is mainly attributable to its correct second-order energy term. While the pp-RPA tends to underestimate absolute correlation energies, it gives good relative energies: much better atomization energies than the ph-RPA, as it has no tendency to underbind, and reaction energies of similar quality. The adiabatic connection in terms of pairing matrix fluctuation paves the way for promising new density functional approximations.

Duke Scholars

Published In

The Journal of chemical physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

May 2014

Volume

140

Issue

18

Start / End Page

18A511

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

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van Aggelen, H., Yang, Y., & Yang, W. (2014). Exchange-correlation energy from pairing matrix fluctuation and the particle-particle random phase approximation. The Journal of Chemical Physics, 140(18), 18A511. https://doi.org/10.1063/1.4865816
Aggelen, Helen van, Yang Yang, and Weitao Yang. “Exchange-correlation energy from pairing matrix fluctuation and the particle-particle random phase approximation.The Journal of Chemical Physics 140, no. 18 (May 2014): 18A511. https://doi.org/10.1063/1.4865816.
van Aggelen H, Yang Y, Yang W. Exchange-correlation energy from pairing matrix fluctuation and the particle-particle random phase approximation. The Journal of chemical physics. 2014 May;140(18):18A511.
van Aggelen, Helen, et al. “Exchange-correlation energy from pairing matrix fluctuation and the particle-particle random phase approximation.The Journal of Chemical Physics, vol. 140, no. 18, May 2014, p. 18A511. Epmc, doi:10.1063/1.4865816.
van Aggelen H, Yang Y, Yang W. Exchange-correlation energy from pairing matrix fluctuation and the particle-particle random phase approximation. The Journal of chemical physics. 2014 May;140(18):18A511.

Published In

The Journal of chemical physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

May 2014

Volume

140

Issue

18

Start / End Page

18A511

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences