Research output: Contribution to Journal/Magazine › Journal article › peer-review

Published

In: Journal of Chemical Physics, Vol. 129, No. 6, ARTN 064105, 14.08.2008.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Peach, MJG, Miller, AM, Teale, AM & Tozer, DJ 2008, 'Adiabatic connection forms in density functional theory: H(2) and the He isoelectronic series', *Journal of Chemical Physics*, vol. 129, no. 6, ARTN 064105. https://doi.org/10.1063/1.2965531

Peach, M. J. G., Miller, A. M., Teale, A. M., & Tozer, D. J. (2008). Adiabatic connection forms in density functional theory: H(2) and the He isoelectronic series. *Journal of Chemical Physics*, *129*(6), Article ARTN 064105. https://doi.org/10.1063/1.2965531

Peach MJG, Miller AM, Teale AM, Tozer DJ. Adiabatic connection forms in density functional theory: H(2) and the He isoelectronic series. Journal of Chemical Physics. 2008 Aug 14;129(6):ARTN 064105. doi: 10.1063/1.2965531

@article{acbdc49b16b74c2285c4f4e0fd3142f6,

title = "Adiabatic connection forms in density functional theory: H(2) and the He isoelectronic series",

abstract = "Full configuration interaction (FCI) data are used to quantify the accuracy of approximate adiabatic connection (AC) forms in describing two challenging problems in density functional theory-the singlet ground state potential energy curve of H(2) in a restricted formalism and the energies of the helium isoelectronic series, H(-) to Ne(8+). For H(2), an exponential-based form yields a potential energy curve that is virtually indistinguishable from the FCI curve, eliminating the unphysical barrier to dissociation observed previously with a [1,1]-Pade-based form and with the random phase approximation. For the helium isoelectronic series, the Pade-based form gives the best overall description, followed by the exponential form, with errors that are orders of magnitude smaller than those from a standard hybrid functional. Particular attention is paid to the limiting behavior of the AC forms with increasing bond distance in H(2) and increasing atomic number in the isoelectronic series; several forms describe both limits correctly. The study illustrates the very high quality results that can be obtained using exchange-correlation functionals based on simple AC forms, when near-exact data are used to determine the parameters in the forms. (C) 2008 American Institute of Physics.",

keywords = "SYSTEMS, 2-ELECTRON, ATOMS, HYDROGEN MOLECULE, PERTURBATION-THEORY, METALLIC SURFACE, ELECTRON-DENSITIES, GROUND-STATE, EXCHANGE-CORRELATION POTENTIALS, CORRELATION-ENERGY",

author = "Peach, {Michael J. G.} and Miller, {Adam M.} and Teale, {Andrew M.} and Tozer, {David J.}",

year = "2008",

month = aug,

day = "14",

doi = "10.1063/1.2965531",

language = "English",

volume = "129",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "AMER INST PHYSICS",

number = "6",

}

TY - JOUR

T1 - Adiabatic connection forms in density functional theory: H(2) and the He isoelectronic series

AU - Peach, Michael J. G.

AU - Miller, Adam M.

AU - Teale, Andrew M.

AU - Tozer, David J.

PY - 2008/8/14

Y1 - 2008/8/14

N2 - Full configuration interaction (FCI) data are used to quantify the accuracy of approximate adiabatic connection (AC) forms in describing two challenging problems in density functional theory-the singlet ground state potential energy curve of H(2) in a restricted formalism and the energies of the helium isoelectronic series, H(-) to Ne(8+). For H(2), an exponential-based form yields a potential energy curve that is virtually indistinguishable from the FCI curve, eliminating the unphysical barrier to dissociation observed previously with a [1,1]-Pade-based form and with the random phase approximation. For the helium isoelectronic series, the Pade-based form gives the best overall description, followed by the exponential form, with errors that are orders of magnitude smaller than those from a standard hybrid functional. Particular attention is paid to the limiting behavior of the AC forms with increasing bond distance in H(2) and increasing atomic number in the isoelectronic series; several forms describe both limits correctly. The study illustrates the very high quality results that can be obtained using exchange-correlation functionals based on simple AC forms, when near-exact data are used to determine the parameters in the forms. (C) 2008 American Institute of Physics.

AB - Full configuration interaction (FCI) data are used to quantify the accuracy of approximate adiabatic connection (AC) forms in describing two challenging problems in density functional theory-the singlet ground state potential energy curve of H(2) in a restricted formalism and the energies of the helium isoelectronic series, H(-) to Ne(8+). For H(2), an exponential-based form yields a potential energy curve that is virtually indistinguishable from the FCI curve, eliminating the unphysical barrier to dissociation observed previously with a [1,1]-Pade-based form and with the random phase approximation. For the helium isoelectronic series, the Pade-based form gives the best overall description, followed by the exponential form, with errors that are orders of magnitude smaller than those from a standard hybrid functional. Particular attention is paid to the limiting behavior of the AC forms with increasing bond distance in H(2) and increasing atomic number in the isoelectronic series; several forms describe both limits correctly. The study illustrates the very high quality results that can be obtained using exchange-correlation functionals based on simple AC forms, when near-exact data are used to determine the parameters in the forms. (C) 2008 American Institute of Physics.

KW - SYSTEMS

KW - 2-ELECTRON

KW - ATOMS

KW - HYDROGEN MOLECULE

KW - PERTURBATION-THEORY

KW - METALLIC SURFACE

KW - ELECTRON-DENSITIES

KW - GROUND-STATE

KW - EXCHANGE-CORRELATION POTENTIALS

KW - CORRELATION-ENERGY

U2 - 10.1063/1.2965531

DO - 10.1063/1.2965531

M3 - Journal article

VL - 129

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 6

M1 - ARTN 064105

ER -