Cited by 384

The DOI matches its Crossref record; 60 of the 60 references it cites were found in a registry or an index.

Influence of Triplet Instabilities in TDDFT

Open access

Peach, Michael J. G., Williamson, Matthew J., Tozer, David J.·2011·Journal of Chemical Theory and Computation

DOI 10.1021/ct200651r

Open this paper in CoChat — free account

Abstract

Singlet and triplet vertical excitation energies from time-dependent density functional theory (TDDFT) can be affected in different ways by the inclusion of exact exchange in hybrid or Coulomb-attenuated/range-separated exchange-correlation functionals; in particular, triplet excitation energies can become significantly too low. To investigate these issues, the explicit dependence of excitation energies on exact exchange is quantified for four representative molecules, paying attention to the effect of constant, short-range, and long-range contributions. A stability analysis is used to verify that the problematic TDDFT triplet excitations can be understood in terms of the ground state triplet instability problem, and it is proposed that a Hartree-Fock stability analysis should be used to identify triplet excitations for which the presence of exact exchange in the TDDFT functional is undesirable. The use of the Tamm-Dancoff approximation (TDA) significantly improves the problematic triplet excitation energies, recovering the correct state ordering in benzoquinone; it also affects the corresponding singlet states, recovering the correct state ordering in naphthalene. The impressive performance of the TDA is maintained for a wide range of molecules across representative functionals.

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

Integrity signals

Registry

Crossref · 10.1021/ct200651r

Cites

60 of 60 references verified0 citation errors · 0 not checkable

Statistics

Claims the paper makes

The claims and statistics of this paper haven’t been checked yet.

Run the check — free, no account needed. It reads the open-access text and checks the sources it cites.

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

The self-check needs the paper’s full text.

Generalized Gradient Approximation Made Simple
Perdew, J. P., Burke, K., & Ernzerhof, M. (1996) · Physical Review Letters · doi:10.1103/physrevlett.77.3865 · Cited by 215,824
Density-functional thermochemistry. III. The role of exact exchange
Becke, A. D. (1993) · The Journal of Chemical Physics · doi:10.1063/1.464913 · Cited by 103,767
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
Lee, C., Yang, W., & Parr, R. G. (1988) · Physical Review B · doi:10.1103/physrevb.37.785 · Cited by 100,874
Self-Consistent Equations Including Exchange and Correlation Effects
Kohn, W., & Sham, L. J. (1965) · Physical Review · doi:10.1103/physrev.140.a1133 · Cited by 64,135
Density-functional exchange-energy approximation with correct asymptotic behavior
Becke, A. D. (1988) · Physical Review A · doi:10.1103/physreva.38.3098 · Cited by 53,711
Inhomogeneous Electron Gas
Hohenberg, P., & Kohn, W. (1964) · Physical Review · doi:10.1103/physrev.136.b864 · Cited by 53,541
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
Stephens, P. J., Devlin, F. J., Chabalowski, C. F., & Frisch, M. J. (1994) · The Journal of Physical Chemistry · doi:10.1021/j100096a001 · Cited by 23,248
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
Vosko, S. H., Wilk, L., & Nusair, M. (1980) · Canadian Journal of Physics · doi:10.1139/p80-159 · Cited by 20,768
A new mixing of Hartree–Fock and local density-functional theories
Becke, A. D. (1993) · The Journal of Chemical Physics · doi:10.1063/1.464304 · Cited by 16,515
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
Yanai, T., Tew, D. P., & Handy, N. C. (2004) · Chemical Physics Letters · doi:10.1016/j.cplett.2004.06.011 · Cited by 14,976
Density-Functional Theory for Time-Dependent Systems
Runge, E., & Gross, E. K. U. (1984) · Physical Review Letters · doi:10.1103/physrevlett.52.997 · Cited by 8,914
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
Valiev, M., Bylaska, E. J., Govind, N., Kowalski, K., Straatsma, T. P., Van Dam, H. J. J., Wang, D., Nieplocha, J., Apra, E., Windus, T. L., et al. (2010) · Computer Physics Communications · doi:10.1016/j.cpc.2010.04.018 · Cited by 5,779
Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory
Bauernschmitt, R., & Ahlrichs, R. (1996) · Chemical Physics Letters · doi:10.1016/0009-2614(96)00440-x · Cited by 5,747
A Simplification of the Hartree-Fock Method
Slater, J. C. (1951) · Physical Review · doi:10.1103/physrev.81.385 · Cited by 4,584
Systematic optimization of long-range corrected hybrid density functionals
Chai, J.-D., & Head-Gordon, M. (2008) · The Journal of Chemical Physics · doi:10.1063/1.2834918 · Cited by 4,054
Note on Exchange Phenomena in the Thomas Atom
Dirac, P. A. M. (1930) · Mathematical Proceedings of the Cambridge Philosophical Society · doi:10.1017/s0305004100016108 · Cited by 3,302
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules
Dreuw, A., & Head-Gordon, M. (2005) · Chemical Reviews · doi:10.1021/cr0505627 · Cited by 2,722
Toward a systematic molecular orbital theory for excited states
Foresman, J. B., Head-Gordon, M., Pople, J. A., & Frisch, M. J. (1992) · The Journal of Physical Chemistry · doi:10.1021/j100180a030 · Cited by 2,386
A long-range correction scheme for generalized-gradient-approximation exchange functionals
Iikura, H., Tsuneda, T., Yanai, T., & Hirao, K. (2001) · The Journal of Chemical Physics · doi:10.1063/1.1383587 · Cited by 2,372
Time-Dependent Density Functional Response Theory for Molecules
CASIDA, M. E. (1995) · Recent Advances in Computational Chemistry · doi:10.1142/9789812830586_0005 · Cited by 2,293
Time-dependent density functional theory within the Tamm–Dancoff approximation
Hirata, S., & Head-Gordon, M. (1999) · Chemical Physics Letters · doi:10.1016/s0009-2614(99)01149-5 · Cited by 2,268
Adiabatic time-dependent density functional methods for excited state properties
Furche, F., & Ahlrichs, R. (2002) · The Journal of Chemical Physics · doi:10.1063/1.1508368 · Cited by 2,244
Universal variational functionals of electron densities, first-order density matrices, and natural spin-orbitals and solution of the v -representability problem
Levy, M. (1979) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.76.12.6062 · Cited by 1,969
A long-range-corrected time-dependent density functional theory
Tawada, Y., Tsuneda, T., Yanagisawa, S., Yanai, T., & Hirao, K. (2004) · The Journal of Chemical Physics · doi:10.1063/1.1688752 · Cited by 1,896
Excitation energies in density functional theory: An evaluation and a diagnostic test
Peach, M. J. G., Benfield, P., Helgaker, T., & Tozer, D. J. (2008) · The Journal of Chemical Physics · doi:10.1063/1.2831900 · Cited by 1,401
Self-citation
Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules
Jacquemin, D., Wathelet, V., Perpète, E. A., & Adamo, C. (2009) · Journal of Chemical Theory and Computation · doi:10.1021/ct900298e · Cited by 1,130
Importance of short-range versus long-range Hartree-Fock exchange for the performance of hybrid density functionals
Vydrov, O. A., Heyd, J., Krukau, A. V., & Scuseria, G. E. (2006) · The Journal of Chemical Physics · doi:10.1063/1.2244560 · Cited by 989
Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3
Schreiber, M., Silva-Junior, M. R., Sauer, S. P. A., & Thiel, W. (2008) · The Journal of Chemical Physics · doi:10.1063/1.2889385 · Cited by 977
Improving virtual Kohn–Sham orbitals and eigenvalues: Application to excitation energies and static polarizabilities
Tozer, D. J., & Handy, N. C. (1998) · The Journal of Chemical Physics · doi:10.1063/1.477711 · Cited by 963
Self-citation
Dynamic polarizabilities and excitation spectra from a molecular implementation of time-dependent density-functional response theory: N2 as a case study
Jamorski, C., Casida, M. E., & Salahub, D. R. (1996) · The Journal of Chemical Physics · doi:10.1063/1.471140 · Cited by 913
Stability analysis for solutions of the closed shell Kohn–Sham equation
Bauernschmitt, R., & Ahlrichs, R. (1996) · The Journal of Chemical Physics · doi:10.1063/1.471637 · Cited by 896
TD-DFT Performance for the Visible Absorption Spectra of Organic Dyes: Conventional versus Long-Range Hybrids
Jacquemin, D., Perpète, E. A., Scuseria, G. E., Ciofini, I., & Adamo, C. (2008) · Journal of Chemical Theory and Computation · doi:10.1021/ct700187z · Cited by 879
Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theory
Stein, T., Kronik, L., & Baer, R. (2009) · Journal of the American Chemical Society · doi:10.1021/ja8087482 · Cited by 870
Combining long-range configuration interaction with short-range density functionals
Leininger, T., Stoll, H., Werner, H.-J., & Savin, A. (1997) · Chemical Physics Letters · doi:10.1016/s0009-2614(97)00758-6 · Cited by 777
Self-consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory
Seeger, R., & Pople, J. A. (1977) · The Journal of Chemical Physics · doi:10.1063/1.434318 · Cited by 710
A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states
Rohrdanz, M. A., Martins, K. M., & Herbert, J. M. (2009) · The Journal of Chemical Physics · doi:10.1063/1.3073302 · Cited by 705
Response functions in the CC3 iterative triple excitation model
Christiansen, O., Koch, H., & Jo/rgensen, P. (1995) · The Journal of Chemical Physics · doi:10.1063/1.470315 · Cited by 579
Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction
Silva-Junior, M. R., Schreiber, M., Sauer, S. P. A., & Thiel, W. (2008) · The Journal of Chemical Physics · doi:10.1063/1.2973541 · Cited by 539
Double-hybrid density functional theory for excited electronic states of molecules
Grimme, S., & Neese, F. (2007) · The Journal of Chemical Physics · doi:10.1063/1.2772854 · Cited by 522
Substantial Errors from Time‐Dependent Density Functional Theory for the Calculation of Excited States of Large π Systems
Grimme, S., & Parac, M. (2003) · ChemPhysChem · doi:10.1002/cphc.200390047 · Cited by 507
Assessment of a Coulomb-attenuated exchange–correlation energy functional
Peach, M. J. G., Helgaker, T., Sałek, P., Keal, T. W., Lutnæs, O. B., Tozer, D. J., & Handy, N. C. (2006) · Phys. Chem. Chem. Phys. · doi:10.1039/b511865d · Cited by 479
Self-citation
Non-Adiabatic Meson Theory of Nuclear Forces
Dancoff, S. M. (1950) · Physical Review · doi:10.1103/physrev.78.382 · Cited by 472
Density Functional Theory with Correct Long-Range Asymptotic Behavior
Baer, R., & Neuhauser, D. (2005) · Physical Review Letters · doi:10.1103/physrevlett.94.043002 · Cited by 439
Simultaneous benchmarking of ground- and excited-state properties with long-range-corrected density functional theory
Rohrdanz, M. A., & Herbert, J. M. (2008) · The Journal of Chemical Physics · doi:10.1063/1.2954017 · Cited by 343
Optoelectronic and Excitonic Properties of Oligoacenes: Substantial Improvements from Range-Separated Time-Dependent Density Functional Theory
Wong, B. M., & Hsieh, T. H. (2010) · Journal of Chemical Theory and Computation · doi:10.1021/ct100529s · Cited by 292
Excitation Energies from Time-Dependent Density Functional Theory for Linear Polyene Oligomers: Butadiene to Decapentaene
Hsu, C.-P., Hirata, S., & Head-Gordon, M. (2001) · The Journal of Physical Chemistry A · doi:10.1021/jp0024367 · Cited by 276
Charge-transfer correction for improved time-dependent local density approximation excited-state potential energy curves: Analysis within the two-level model with illustration for H2 and LiH
Casida, M. E., Gutierrez, F., Guan, J., Gadea, F.-X., Salahub, D., & Daudey, J.-P. (2000) · The Journal of Chemical Physics · doi:10.1063/1.1313558 · Cited by 259
Benchmarks of electronically excited states: Basis set effects on CASPT2 results
Silva-Junior, M. R., Schreiber, M., Sauer, S. P. A., & Thiel, W. (2010) · The Journal of Chemical Physics · doi:10.1063/1.3499598 · Cited by 246
Charge-Transfer-Like π→π* Excitations in Time-Dependent Density Functional Theory: A Conundrum and Its Solution
Kuritz, N., Stein, T., Baer, R., & Kronik, L. (2011) · Journal of Chemical Theory and Computation · doi:10.1021/ct2002804 · Cited by 243
Über die Zahl der Dispersionselektronen, die einem stationären Zustande zugeordnet sind. (Vorläufige Mitteilung)
Thomas, W. (1925) · Die Naturwissenschaften · doi:10.1007/bf01558908 · Cited by 241
Coulomb-attenuated exchange energy density functionals
GILL, P. M. W., ADAMSON, R. D., & POPLE, J. A. (1996) · Molecular Physics · doi:10.1080/00268979609484488 · Cited by 228
Assessment of Functionals for TD-DFT Calculations of Singlet−Triplet Transitions
Jacquemin, D., Perpète, E. A., Ciofini, I., & Adamo, C. (2010) · Journal of Chemical Theory and Computation · doi:10.1021/ct100005d · Cited by 227
Dalton, a molecular electronic structure program, Release Dalton2011
Angeli, C., Bak, K. L., Bakken, V., Ove Christiansen, A., Cimiraglia, R., Coriani, S., Dahle, P., Dalskov, E. K., Enevoldsen, T., Fernández, B. F., et al. (2011) · Cited by 181
Assessment of the ωB97 family for excited-state calculations
Jacquemin, D., Perpète, E. A., Ciofini, I., & Adamo, C. (2011) · Theoretical Chemistry Accounts · doi:10.1007/s00214-010-0783-x · Cited by 176
Troubleshooting time-dependent density-functional theory for photochemical applications: Oxirane
Córdova, F., Joubert-Doriol, L., Ipatov, A. N., Casida, M. E., Filippi, C., & Vela, A. (2007) · The Journal of Chemical Physics · doi:10.1063/1.2786997 · Cited by 153
TDDFT diagnostic testing and functional assessment for triazene chromophores
Peach, M. J., Sueur, C. R. L., Ruud, K., Guillaume, M., & Tozer, D. J. (2009) · Physical Chemistry Chemical Physics · doi:10.1039/b822941d · Cited by 150
Self-citation
Assessment of dressed time-dependent density-functional theory for the low-lying valence states of 28 organic chromophores
Huix‐Rotllant, M., Ipatov, A. N., Rubio, Á., & Casida, M. E. (2011) · Chemical Physics · doi:10.1016/j.chemphys.2011.03.019 · Cited by 96
Density Functional Theory of Time-Dependent Systems
Gross, E. K. U., Ullrich, C. A., & Gossmann, U. J. (1995) · NATO ASI series. Series B : Physics · doi:10.1007/978-1-4757-9975-0_7 · Cited by 78
Improving the TDDFT calculation of low‐lying excited states for polycyclic aromatic hydrocarbons using the Tamm–Dancoff approximation
Wang, Y., & Wu, G. (2007) · International Journal of Quantum Chemistry · doi:10.1002/qua.21510 · Cited by 73
Dissociation of hydrogen and nitrogen molecules studied using density functional theory
Lee, A. M., & Handy, N. C. (1993) · Journal of the Chemical Society Faraday Transactions · doi:10.1039/ft9938903999 · Cited by 33

TD-DFT benchmarks: A review
Laurent, A. D., & Jacquemin, D. (2013) · International Journal of Quantum Chemistry · doi:10.1002/qua.24438 · Cited by 1,382
The theory of thermally activated delayed fluorescence for organic light emitting diodes
Penfold, T. J., Dias, F. B., & Monkman, A. P. (2018) · Chemical Communications · doi:10.1039/c7cc09612g · Cited by 341
Substituent effects on absorption spectra of pH indicators: an experimental and computational study of sulfonphthaleine dyes
De Meyer, T., Hemelsoet, K., Van Speybroeck, V., & De Clerck, K. (2014) · Dyes and Pigments · doi:10.1016/j.dyepig.2013.10.048 · Cited by 107

See all 384

Authors: Peach, M. J. G., Williamson, M. J., & Tozer, D. J.
Venue: Journal of Chemical Theory and Computation
Publisher: American Chemical Society (ACS)
Published: 2011-10-19
Volume: 7
Issue: 11
Pages: 3578-3585
ISSN: 1549-9618 (ISSN-L)
1549-9626
DOI: 10.1021/ct200651r
OpenAlex: W2076757103
Cited by: 384
References: 60
FWCI: 7.47
Type: journal article
Language: en
Open access: green

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review

Data sources

Bibliographic data: Semantic Scholar, OpenAlex, Crossref.

Contains information from the Semantic Scholar Academic Graph Datasets, made available under the ODC Attribution License (ODC-BY 1.0).

Semantic Scholar’s data is described in: Kinney, R., et al. (2023). The Semantic Scholar Open Data Platform. arXiv:2301.10140.

Influence of Triplet Instabilities in TDDFT

Abstract

Overview

Integrity signals

Verification

Claims the paper makes

Self-check

Citations

Cites

Cited by

Metadata

Record

About these checks

Data sources