Behavior of density functionals with respect to basis set. VI. Truncation of the correlation consistent basis sets

Prascher, Brian P.; Wilson, Brent R.; Wilson, Angela K.

doi:10.1063/1.2768602

Cited by 20 publications

(14 citation statements)

References 31 publications

(26 reference statements)

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“…[1][2][3][4][5] The approach provides optical properties and excitation energies in good agreement with experiment when using standard basis sets. [6][7][8][9][10][11][12] The basis-set dependence of density functional theory ͑DFT͒ calculations on molecular ground-state ͑GS͒ properties has recently been investigated, 13,14 whereas much less is known about the accuracy and basis-set requirements of TDDFT calculations on ESs. 15,16 The use of the same functionals as employed in GS DFT calculations leads to some general shortcomings of the TDDFT approach.…”

Section: Introductionmentioning

confidence: 99%

Coupled-cluster and density functional theory studies of the electronic excitation spectra of trans-1,3-butadiene and trans-2-propeniminium

Lehtonen

Sundholm

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et al. 2009

The Journal of Chemical Physics

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The electronic excitation spectra of trans-1,3-butadiene (CH(2)=CH-CH=CH(2)) and trans-2-propeniminium (CH(2)=CH-CH=NH(2)(+)) have been studied at several coupled-cluster and time-dependent density functional theory levels using the linear response approach. Systematic studies employing large correlation-consistent basis sets show that approximate singles and doubles coupled-cluster calculations yield excitation energies in good agreement with experiment for all states except for the two lowest excited A(g) states of trans-1,3-butadiene which have significant multiconfigurational character. Time-dependent density functional theory calculations employing the generalized gradient approximation and hybrid functionals yield too low excitation energies in the basis set limit. In trans-1,3-butadiene, increasing the basis set size by augmenting multiple diffuse functions is observed to reduce the high-lying excitation energies with most density functionals. The decrease in the energies is connected to the incorrect asymptotic behavior of the exchange-correlation potential. The results also demonstrate that standard density functionals are not capable of providing excitation energies of sufficient accuracy for experimental assignments.

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Section: Introductionmentioning

confidence: 99%

Coupled-cluster and density functional theory studies of the electronic excitation spectra of trans-1,3-butadiene and trans-2-propeniminium

Lehtonen

Sundholm

Send

et al. 2009

The Journal of Chemical Physics

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“…Recently, it was demonstrated that modern meta‐GGA density functionals have greater accuracy in EA values 5–7. At the same time, it is known that a basis set also has an important impact on computed EA values 8, 9. In particular, it was noted9 that diffuse s ‐ and p ‐functions are very important for correct electron affinity prediction, even more important than diffuse polarization functions.…”

Section: Introductionmentioning

confidence: 99%

Exploration of density functional methods for one‐electron reduction potential of nitrobenzenes

Zubatyuk

Gorb²,

Шишкин

et al. 2009

J Comput Chem

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Performance of the set of density functional approaches for calculation of one-electron reduction potentials of nitroaromatic compounds was investigated. To select the most precise and affordable method, we selected a set of model molecules and investigated effects of basis set, density functional, and solvation model on the calculation of reduction potentials. It was found that the mPWB1K/TZVP method provides the most accurate gas phase electron affinity values (RMS error is 0.1 eV). This method in conjunction with the PCM (Bondi) method yields also the most accurate difference in solvation energies of neutral oxidized form and anion-radical reduced form. The final E0 values were calculated with RMS error of 0.10 V, compared with experimental values.

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“…When using FNOs based on the MBPT͑2͒ density matrix, 29,30 this truncated orbital set has been shown to be surprisingly effective at truncating larger basis sets, allowing ϳ50% of a modified unoccupied orbital set to be removed without significant changes to ground state CC energies and density matrices. [18][19][20] The FNO procedure could be combined with further reductions in the underlying contracted Gaussian basis [31][32][33] for further savings.…”

Section: Introductionmentioning

confidence: 99%

Frozen natural orbital coupled-cluster theory: Forces and application to decomposition of nitroethane

Taube

Bartlett

2008

The Journal of Chemical Physics

116

128

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The frozen natural orbital ͑FNO͒ coupled-cluster method increases the speed of coupled-cluster ͑CC͒ calculations by an order of magnitude with no consequential error along a potential energy surface. This method allows the virtual space of a correlated calculation to be reduced by about half, significantly reducing the time spent performing the coupled-cluster ͑CC͒ calculation. This paper reports the derivation and implementation of analytical gradients for FNO-CC, including all orbital relaxation for both noncanonical and semicanonical perturbed orbitals. These derivatives introduce several new orbital relaxation contributions to the CC density matrices. FNO-CCSD͑T͒ and FNO-⌳CCSD͑T͒ are applied to a test set of equilibrium structures, verifying that these methods are capable of reproducing geometries and vibrational frequencies accurately, as well as energies. Several decomposition pathways of nitroethane are investigated using CCSD͑T͒ and ⌳CCSD͑T͒ with 60% of the FNO virtual orbitals in a cc-pVTZ basis, and find differences on the order of 5 kcal/ mol with reordering of the transition state energies when compared to B3LYP 6-311 +G͑3df ,2p͒.

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Behavior of density functionals with respect to basis set. VI. Truncation of the correlation consistent basis sets

Cited by 20 publications

References 31 publications

Coupled-cluster and density functional theory studies of the electronic excitation spectra of trans-1,3-butadiene and trans-2-propeniminium

Coupled-cluster and density functional theory studies of the electronic excitation spectra of trans-1,3-butadiene and trans-2-propeniminium

Exploration of density functional methods for one‐electron reduction potential of nitrobenzenes

Frozen natural orbital coupled-cluster theory: Forces and application to decomposition of nitroethane

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