Functional Assessment for Predicting Charge-Transfer Excitations of Dyes in Complexed State: A Study of Triphenylamine–Donor Dyes on Titania for Dye-Sensitized Solar Cells

Dev, Pratibha; Agrawal, Saurabh; English, Niall J.

doi:10.1021/jp306153e

Cited by 50 publications

(33 citation statements)

References 48 publications

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“…It may be the case that molecular simulation [36]-especially in its guise of Density Functional Theory (DFT)-can deal with complicated chemical reactions in disparate electronic milieu of different atomistic environments of hydrides in heterogeneous scaffold environments; indeed, this may be able to optimise further materials design and selection. However, the appropriate selection and careful benchmarking and tailoring of DFT functionals in interfacial systems [37] will be very important in this vein, to ensure the highest quality of interatomic interactions, as well as in molecular simulation handling the wider challenge of handling possible hydrogen bonding accurately [38], which may well be important in some promising classes of hydrogen storage materials.…”

Section: Discussionmentioning

confidence: 99%

In Situ Formation of Metal Hydrides Inside Carbon Aerogel Frameworks for Hydrogen Storage Applications

Ghaani

Alam

Catti

et al. 2020

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Nano-confined chemical reactions bear great promise for a wide range of important applications in the near-to-medium term, e.g., within the emerging area of chemical storage of renewable energy. To explore this important trend, in the present work, resorcinol-/formaldehyde-based carbon aerogels were prepared by sol-gel polymerisation of resorcinol, with furfural catalysed by a sodium-carbonate solution using ambient-pressure drying. These aerogels were further carbonised in nitrogen to obtain their corresponding carbon aerogels. Through this study, the synthesis parameters were selected in a way to obtain minimum shrinkage during the drying step. The microstructure of the product was observed using Scanning Electron Microscopy (SEM) and Field Emission Scanning Electron Microscopy (FESEM) imaging techniques. The optimised carbon aerogels were found to have pore sizes of ~21 nm with a specific accessible surface area equal to 854.0 m2/g. Physical activation of the carbon aerogel with CO2 generates activated carbon aerogels with a surface area of 1756 m2/g and a total porosity volume up to 3.23 cm3/g. The product was then used as a scaffold for magnesium/cobalt-hydride formation. At first, cobalt nanoparticles were formed inside the scaffold, by reducing the confined cobalt oxide, then MgH2 was synthesised as the second required component in the scaffold, by infiltrating the solution of dibutyl magnesium (MgBu2) precursor, followed by a hydrogenation reaction. Further hydrogenation at higher temperature leads to the formation of Mg2CoH5. In situ synchrotron X-ray diffraction was employed to study the mechanism of hydride formation during the heating process.

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Section: Discussionmentioning

confidence: 99%

In Situ Formation of Metal Hydrides Inside Carbon Aerogel Frameworks for Hydrogen Storage Applications

Ghaani

Alam

Catti

et al. 2020

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“…This strongly indicates that the functional choice is highly system-specific, as suggested by De Angelis and others. 14, [88][89][90] In summary, the accuracy of the estimated parameters (i.e., GSOP and ESOP) is 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 It is not easy to find a single LAC structure that shows the most desirable values of LHE, inject G ∆ and CB ∆ . The balance of these parameters might be essential for achieving high performance.…”

Section: Properties Of Lac Dyesmentioning

confidence: 99%

Computational Investigation of Acene-Modified Zinc-Porphyrin Based Sensitizers for Dye-Sensitized Solar Cells

Liu

Guan

et al. 2015

J. Phys. Chem. C

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A series of acene-modified zinc-porphyrin dyes (benzene to pentacene, denoted as LAC-1 to were chosen to examine their performance as photosensitizers in dye-sensitized solar cells (DSSCs). Their structural, electronic and optical properties were investigated at the DFT/TDDFT levels using various theoretical models (i.e., the gas phase model and the implicit/explicit solvent model). The Dye@TiO 2 complex was used to investigate the dye/semiconductor interfaces using both the cluster and periodic models. After a careful examination of the dependence of the results on different theoretical approaches, some basic principles could be derived based on the theoretical investigation of structure-function relationships in isolated dyes and dye-TiO 2 assemblies. Based on these ideas, some general suggestions can be proposed for the future design of dyes for use in DSSCs. For instance, the DFT functionals used in estimating the critical parameters for DSSCs should be carefully validated.Sometimes the performances of the DFT functionals can be improved by a specific energy-shift correction to compensate for systematic errors. Benchmark calculations indicated that the best approach for depicting the reduction potentials is either the M06-2X functional combined with the formula ∆E red = (E 0 -E -) GS or the B3LYP functional combined with Koopman's Theorem. The best functional for estimating the excitation energies was found to be LC-ωPBE. The impact of significant thermal fluctuations on the optoelectronic properties of dyes may also be an important consideration in the prediction of more efficient dyes for use DSSCs. In contrast to the selection of DFT functionals, both the cluster and periodic models resulted in consistent views of the dye-TiO 2 interactions, indicating that the use of either model should achieve reasonable results at least in the qualitative manner.

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“…Given striking progress in Density Functional Theory (DFT)-based molecular simulation, particularly ab-initio molecular dynamics (AIMD), as an initial 'screening' technique in materials design, especially in the context of DSCs, [5][6][7] with critical assessment of optimal choice of functionals being sine qua non, 6,7 we have applied such approaches in to reveal important dispersion and solvation effects on both dye structure and binding modes at dye/substrate surfaces, with reasonable reproduction of essential electronic properties, such as band gap. [8][9][10] We have applied this extensively to a prototypical N719-chromophore adsorbed to an anatasetitania (101) interface, assessing vibrational and structural characteristics in the presence of a…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Molecular Dynamics Studies of the Effect of Solvation by Room-Temperature Ionic Liquids on the Vibrational Properties of a N719-Chromophore/Titania Interface

2018

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The accurate ab-initio modelling of prototypical and well-representative photo-active interfaces for candidate dye-sensitised solar cells (DSCs) is a perennial problem in physical chemistry. To this end, using ab-initio, density functional theory (DFT)-based molecular dynamics (AIMD) has been carried out here to investigate the effect with which the choice of functional has on a system mimicking the essential workings of a DSC: the energetic properties of a [bmim] + [NTf2]room-temperature ionic liquid (RTIL), solvating a N719-sensitising dye adsorbed onto an anatase-titania (101) surface were scrutinised. In so doing, we glean important insights into how using a RTIL as the electrolytic hole acceptor alters and modulates the dynamical properties of the widely-used N719 dye. A fully crossed study has been carried out comparing the BLYP and PBE functionals, both unsolvated and solvated by the RTIL, both with and without Grimme D3 dispersion corrections. Also, vibrational spectra for the photo-active interface in the DSC configuration were calculated by means of Fourier-transforming atomic mass-weighted velocity autocorrelation functions. The ab-initio vibrational spectra were compared with high-quality experimental data and against each other; the effect of various methodological choices on the vibrational spectra were also studied, with PBE generally performed best in producing spectra which matched the experimental frequency modes typically expected.

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Functional Assessment for Predicting Charge-Transfer Excitations of Dyes in Complexed State: A Study of Triphenylamine–Donor Dyes on Titania for Dye-Sensitized Solar Cells

Cited by 50 publications

References 48 publications

In Situ Formation of Metal Hydrides Inside Carbon Aerogel Frameworks for Hydrogen Storage Applications

In Situ Formation of Metal Hydrides Inside Carbon Aerogel Frameworks for Hydrogen Storage Applications

Computational Investigation of Acene-Modified Zinc-Porphyrin Based Sensitizers for Dye-Sensitized Solar Cells

Ab Initio Molecular Dynamics Studies of the Effect of Solvation by Room-Temperature Ionic Liquids on the Vibrational Properties of a N719-Chromophore/Titania Interface

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