Comparison of DFT Methods for Molecular Orbital Eigenvalue Calculations

Zhang, Gang; Musgrave, Charles B.

doi:10.1021/jp061633o

Cited by 774 publications

(585 citation statements)

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“…Calculations were done both in vacuum and with an implicit solvent model of acetonitrile, using ORCA's version of the COSMO method [62]. After geometry optimization, time-dependent DFT calculations were carried out to determine the UV-vis spectra and the HOMO-LUMO gap [42], together with harmonic frequency calculations to evaluate the IR and Raman spectra. The plots of the HOMO and LUMO orbitals were made with the VMD program [63].…”

Section: Methodsmentioning

confidence: 99%

“…The cyclic voltammogram of 1 in CH 3 CN displays a reversible rsfs.royalsocietypublishing.org Interface Focus 5: 20140083 potentials can be approximated to the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, respectively (figure 2b), calculated using quantum chemistry (density functional theory (DFT)) to be separated by 2.1 eV. This value was determined as the lowest energy from the UV-vis spectrum evaluated using a time-dependent DFT method [42]. Plots of the HOMO and LUMO are shown in figure 2b, whereas the calculated spectrum is shown in the electronic supplementary material.…”

Section: Synthesis and Characterization Of A Push -Pull Organic Dyementioning

confidence: 99%

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Dye-sensitized PS- b -P2VP-templated nickel oxide films for photoelectrochemical applications

et al. 2015

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Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p-type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene-block-poly-(2-vinylpyridine) (PS-b-P2VP) diblock copolymer-templated NiO films with an organic push -pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material templated by F108 triblock copolymers. We conclude that NiO films are promising materials for the construction of dye-sensitized photocathodes to be inserted into photoelectrochemical (PEC) cells. However, a combined effort at the interface between materials science and molecular chemistry, ideally funded within a Global Artificial Photosynthesis Project, is still needed to improve the overall performance of the photoelectrodes and progress towards economically viable PEC devices.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesis and Characterization Of A Push -Pull Organic Dyementioning

confidence: 99%

Dye-sensitized PS- b -P2VP-templated nickel oxide films for photoelectrochemical applications

et al. 2015

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“…65 Zhang and Musgrave have also reported that B3LYP yields lower errors in the LUMO energy of small organic molecules as compared to other DFT methods with a higher percentage of Hartree-Fock exchange. 66 The 6-31+G* basis set is recommended in calculations involving anionic species and was therefore used here. 62 The spatial variation of the electron coupling has been scanned as a function of the x-and y-axes displacement at fixed z = 3.4 Å.…”

Section: Methodsmentioning

confidence: 99%

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

et al. 2015

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We theoretically describe in this work the n-type semiconducting behavior of a set of bis(arylene-ethynylene)-s-tetrazines ((ArCC) 2 Tz), by comparing their electronic properties with those of their parent diaryl-s-tetrazines (Ar 2 Tz) after the introduction of ethynylene bridges. The significantly reduced internal reorganization energy for electron transfer is ascribed to an extended delocalization of the LUMO for (ArCC) 2 Tz as opposite to that for Ar 2 Tz, which was described mostly localized on the s-tetrazine ring. The largest electronic coupling and the corresponding electron transfer rates found 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 for bis(phenyl-ethynylene)-s-tetrazine, as well as for some halogenated derivatives, are comparable to those reported for the best performing n-type organic semiconductors materials such as diimides and perylenes. The theoretical mobilities for the studied compounds turn out to be in the range 0.3 -1.3 cm 2 V −1 s −1 , close to values experimentally determined for common n-type organic semiconductors used in real devices. In addition, ohmic contacts can be expected when these compounds are coupled to metallic cathodes such as Na, Ca and Sm. For these reasons, the future application of semiconducting bis(phenyl-ethynylene)-s-tetrazine and its fluorinated and brominated derivatives in optoelectronic devices is envisioned.

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“…Therefore, the exchange-correlation functional describing the many-body electron interactions is approximated for simplification [1]. However, the functional choice is a very responsible stage, because different functionals may describe various characteristics of a substance in different ways, and the results obtained may not be consistent with each other [2,3]. This is especially true for the nanostructures with a complex carbon-nitrogen atomic structures [4 -9].…”

Section: Introductionmentioning

confidence: 99%

Effect of DFT-functional on the energy and electronic characteristics of carbon compounds with the unconventional geometry of the framework

Новиков¹,

Maslov²,

Katin³

et al. 2017

LoM

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We report how strongly the energy and electronic properties of carbon nanostructures with the unconventional framework calculated by means of density functional theory (DFT) depend on the choice of DFT-functional on the example of carbon [n,5]prismanes. For comparative analysis we used such characteristics of molecular system as the values of binding energy and energy difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap). We obtained the binding energies and HOMO-LUMO gaps using seven different functionals B3LYP, X3LYP, M11, B3PW91, PBE0, PW, PBE, which belong to generalized gradient approximation and hybrid functionals, and standard 6-31G(d) electronic basis set. We show that the binding energies obtained for the long [n,5]prismanes with the efficient length of ~150 Å within the various DFT-functionals can differ by a factor of 1.1, and corresponding HOMO-LUMO gaps can differ by a factor of 23. Additional precision calculations at CCSD(T) level of theory of [2,5]prismane allow us to conclude that for determining the binding energies of carbon nanostructures with the unconventional framework, the hybrid functionals B3LYP, X3LYP, and M11 are the best choice, whereas for the HOMO-LUMO gap estimation M11 gives the closest to CCSD(T) result. The reported study is of methodological interest for carrying out the correct DFT-calculations with respect to novel nanomaterials with unconventional carbon framework such as hypercubane system, fullerene composites or pillared graphene.

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Comparison of DFT Methods for Molecular Orbital Eigenvalue Calculations

Cited by 774 publications

References 46 publications

Dye-sensitized PS- b -P2VP-templated nickel oxide films for photoelectrochemical applications

Dye-sensitized PS- b -P2VP-templated nickel oxide films for photoelectrochemical applications

Bis(arylene-ethynylene)-s-tetrazines: A Promising Family of n-Type Organic Semiconductors?

Effect of DFT-functional on the energy and electronic characteristics of carbon compounds with the unconventional geometry of the framework

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