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Illustration of a TDDFT spatial overlap diagnostic by basis function exponent scaling

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Illustration of a TDDFT spatial overlap diagnostic by basis function exponent scaling. / Peach, Michael J. G.; Tozer, David J.

In: Journal of Molecular Structure: THEOCHEM, Vol. 914, No. 1-3, 30.11.2009, p. 110-114.

Research output: Contribution to journalJournal articlepeer-review

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Peach, MJG & Tozer, DJ 2009, 'Illustration of a TDDFT spatial overlap diagnostic by basis function exponent scaling', Journal of Molecular Structure: THEOCHEM, vol. 914, no. 1-3, pp. 110-114. https://doi.org/10.1016/j.theochem.2009.03.009

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Author

Peach, Michael J. G. ; Tozer, David J. / Illustration of a TDDFT spatial overlap diagnostic by basis function exponent scaling. In: Journal of Molecular Structure: THEOCHEM. 2009 ; Vol. 914, No. 1-3. pp. 110-114.

Bibtex

@article{3bb3b6fb11684ee0ab38f19b33759cac,
title = "Illustration of a TDDFT spatial overlap diagnostic by basis function exponent scaling",
abstract = "The relationship between TDDFT vertical excitation energy accuracy and the degree of occupied-virtual spatial orbital overlap is investigated for the CO molecule, by systematically controlling the overlap through a scaling of the basis function exponents. Increasing the scaling parameter contracts the basis set, increasing the overlap values. The corresponding excitation energies also increase and become more accurate, relative to approximate second-order coupled cluster values determined using the same, scaled basis. For the 36 data points (four excitations, each evaluated using nine exponent scaling parameters) there is a strong correlation between excitation energy accuracy and orbital overlap with a generalised gradient approximation functional. Similar correlation is observed with a hybrid and Coulomb-attenuated functional, but the errors become progressively smaller due to their increased fraction of exact, non-local exchange at long-range. The results are fully consistent with the diagnostic test of J. Chem. Phys. 128 (2008) 044118. (C) 2009 Elsevier B.V. All rights reserved.",
keywords = "TRANSFER EXCITED-STATES, Density functional theory, TDDFT, Rydberg states, LOCAL-DENSITY, EXCHANGE, APPROXIMATION, MODEL, ORGANIC-COMPOUNDS, AB-INITIO, EXCITATION-ENERGIES, ABSORPTION, ASYMPTOTICALLY CORRECTED POTENTIALS",
author = "Peach, {Michael J. G.} and Tozer, {David J.}",
year = "2009",
month = nov,
day = "30",
doi = "10.1016/j.theochem.2009.03.009",
language = "English",
volume = "914",
pages = "110--114",
journal = "Journal of Molecular Structure: THEOCHEM",
issn = "0166-1280",
publisher = "Elsevier",
number = "1-3",

}

RIS

TY - JOUR

T1 - Illustration of a TDDFT spatial overlap diagnostic by basis function exponent scaling

AU - Peach, Michael J. G.

AU - Tozer, David J.

PY - 2009/11/30

Y1 - 2009/11/30

N2 - The relationship between TDDFT vertical excitation energy accuracy and the degree of occupied-virtual spatial orbital overlap is investigated for the CO molecule, by systematically controlling the overlap through a scaling of the basis function exponents. Increasing the scaling parameter contracts the basis set, increasing the overlap values. The corresponding excitation energies also increase and become more accurate, relative to approximate second-order coupled cluster values determined using the same, scaled basis. For the 36 data points (four excitations, each evaluated using nine exponent scaling parameters) there is a strong correlation between excitation energy accuracy and orbital overlap with a generalised gradient approximation functional. Similar correlation is observed with a hybrid and Coulomb-attenuated functional, but the errors become progressively smaller due to their increased fraction of exact, non-local exchange at long-range. The results are fully consistent with the diagnostic test of J. Chem. Phys. 128 (2008) 044118. (C) 2009 Elsevier B.V. All rights reserved.

AB - The relationship between TDDFT vertical excitation energy accuracy and the degree of occupied-virtual spatial orbital overlap is investigated for the CO molecule, by systematically controlling the overlap through a scaling of the basis function exponents. Increasing the scaling parameter contracts the basis set, increasing the overlap values. The corresponding excitation energies also increase and become more accurate, relative to approximate second-order coupled cluster values determined using the same, scaled basis. For the 36 data points (four excitations, each evaluated using nine exponent scaling parameters) there is a strong correlation between excitation energy accuracy and orbital overlap with a generalised gradient approximation functional. Similar correlation is observed with a hybrid and Coulomb-attenuated functional, but the errors become progressively smaller due to their increased fraction of exact, non-local exchange at long-range. The results are fully consistent with the diagnostic test of J. Chem. Phys. 128 (2008) 044118. (C) 2009 Elsevier B.V. All rights reserved.

KW - TRANSFER EXCITED-STATES

KW - Density functional theory

KW - TDDFT

KW - Rydberg states

KW - LOCAL-DENSITY

KW - EXCHANGE

KW - APPROXIMATION

KW - MODEL

KW - ORGANIC-COMPOUNDS

KW - AB-INITIO

KW - EXCITATION-ENERGIES

KW - ABSORPTION

KW - ASYMPTOTICALLY CORRECTED POTENTIALS

U2 - 10.1016/j.theochem.2009.03.009

DO - 10.1016/j.theochem.2009.03.009

M3 - Journal article

VL - 914

SP - 110

EP - 114

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

SN - 0166-1280

IS - 1-3

ER -