TD-DFT Vibronic Couplings in Anthraquinones: From Basis Set and Functional Benchmarks to Applications for Industrial Dyes

The use of density functional theory (DFT) and timedependent DFT (TD-DFT) to study the photochemistry of metal complexes is becoming increasingly important among chemists. Computational methods provide unique information on the electronic nature of excited states and their atomic structure, integrating spectroscopy observations on transient species and excited-state dynamics. In this contribution, we present an overview on photochemically active transition metal complexes investigated by DFT. In particular, we discuss a representative range of systems studied up to now, which include CO-and NO-releasing inorganic and organometallic complexes, haem and haem-like complexes dissociating small diatomic molecules, photoactive anti-cancer Pt and Ru complexes, Ru polypyridyls and diphosphino Pt derivatives.

show abstract

“…Several studies have thoroughly investigated such dependence, highlighting the importance of careful benchmarking work [131][132][133][134].…”

Section: Discussionmentioning

confidence: 99%

The photochemistry of transition metal complexes using density functional theory

Garino

Salassa

2013

Phil. Trans. R. Soc. A.

View full text Add to dashboard Cite

show abstract

“…They are followed by modern and highly parameterized range-separated hybrids belonging to the !B97 family of ECFs, which are often underlined in the literature as promising approaches to model several other chemical properties, 11,27,31 Another interesting issue arising from Figure 1 concerns the performance of the Minnesota density-functionals 8 excluding the already mentioned SOGGA11-X. First generation densityfunctionals (e.g., M05, M06) are more accurate than those belonging to the second one (e.g, M11, N12-SX, MN12-SX).…”

Section: -8mentioning

confidence: 99%

“…They are followed by modern and highly parameterized range-separated hybrids belonging to the !B97 family of ECFs, which are often underlined in the literature as promising approaches to model several other chemical properties, 11,27,31 Table S4 in the Supporting Information for more details). As a general trend, CC and CO bond lengths are underestimated (negative mean deviations) while CH ones are often overestimated In order to verify the existence of a relationship between the performances obtained for structural parameters and energetic properties, we plot in Figure 4 the errors for the properties.…”

Section: -8mentioning

confidence: 99%

Benchmarking Density Functionals on Structural Parameters of Small-/Medium-Sized Organic Molecules

Brémond

Savarese

et al. 2016

J. Chem. Theory Comput.

Self Cite

184

134

View full text Add to dashboard Cite

In this letter we report the error analysis of 59 exchange-correlation functionals in evaluating the structural parameters of small-and medium-sized organic molecules.From this analysis, recently developed double-hybrids, such as xDH-PBE0, emerge as the most reliable methods, while global-hybrids confirm their robustness in reproducing molecular structures. Notably the M06-L density-functional is the only semilocal method reaching an accuracy comparable to hybrids'. A comparison with errors obtained on energetic databases (including thermochemistry, reaction barriers and interaction energies) indicate that most of the functionals have a coherent behavior, showing low (or high) deviations on both energy and structure datasets. Only a few of them are more prone toward one of these two properties. 2The quality of any method rooted in density functional theory (DFT) is (strongly) affected by the choice of the exchange-correlation functional (ECF), which gives the unknown term of the Kohn-Sham energy. If from one side the spreading of DFT in chemistry and physics has encouraged the research of new and better-performing density-functionals, 1 from the other side their validation has become a due step before any routine application. Such a benchmark passes through a careful evaluation (and consequent statistical analysis) of the errors on defined properties and systems sets.Starting from the nineties, a large effort has been made in order to define standard benchmark sets allowing for a meaningful and fair comparison between different ECFs. 2-8Among the properties firstly targeted, atomization energies, ionization potentials and electron affinities 2-4 as well as bond lengths and angles of (mostly) small organic systems received a particular attention. Figure S1 and S2 in the Supporting Information). Both databases are an excellent diagnostic test to discriminate density-functionals in modeling structural parameters of organic systems.In this Letter, we use these two datasets to thoroughly benchmark the accuracy of 59ECFs (reported in Table The references and further details of all the considered computational methods involved in this Letter are given in Table S1 of the Supporting Information.In order to discriminate the accuracy of the selected approaches, we define a criterion based on the matrix containing all the interatomic distances. For each system, we compute the mean absolute deviation (MAD) over the distance matrix of the probed and the reference geometries, and calculate the averaged deviation over the set. Figure 1 reports these statistics for the 63 computational approaches considered in this Letter (see Table S2 and S3 in the Supporting Information for more details).For the CCse21 dataset, the deviations span from 0.002 to 0.016 Å for xDH-PBE0and HF methods, respectively. Within this interval, a smooth transition from high to low accuracy is observed. Apart from the worst performing ECFs like BLYP, B97D, B97D3 or TPSS, most of the methods give a slight increase of the distance matrix deviation (...

show abstract

“…Although previous studies [64]- [66] about the global hybrids such as PBE0 and B3LYP, have been found efficient within the vertical time dependent DFT approximation for some of dyes but in DCM case the mPW1PBE and mPW1LYP are more efficient. Estimated transition energies by other functionals have large deviation from experimental results.…”

Section: A Functional Investigationmentioning

confidence: 81%

“…The efficiency of mPW1PBE to discussion of electronic transition in DCM was proved in previous section. One of the vast investigations aiming at assessing the influence of the size of the some Pople basis on the TD-DFT calculation and topology of the vibronic band has been done by Jacquemin [64] and Grimme [63] on the other dyes. At the present work almost all selected basis give similar outcomes analogous to [64].…”

Section: B Basis Set Investigationmentioning

confidence: 99%

Absorption of DCM Dye in Ethanol: Experimental and Time Dependent Density Functional Study

Nabavi

Khodabandeh

Golbabaee

et al. 2018

IJOP

View full text Add to dashboard Cite

ABSTRACT-Experimental and theoretical absorption spectra of [2-[2-[4-(dimethylamino) phenyl]ethenyl]-6-methyl-4H-pyran-4-ylidene]-propanedinitrile (DCM) have been studied. UVVisible (UV-Vis.) absorption spectrum of DCM has been reported after its synthesis. Two relatively intense peaks appeared at 473 and 362 nm respectively. A theoretical investigation on the electronic structure of DCM is presented in an effort to rationalize our experimental results. Theoretical results have been obtained with a polarizable continuum model timedependent density functional theory (PCM-TD-DFT) approach. At first, a vast functional benchmark has been performed to determine a suitable approach for determination of electronic structure and UV-Vis. absorption spectrum of DCM. In a second step, we evaluated the impact of the atomic basis set on the electronic transition energies using a large panel of Pople's basis sets ,up to the 6-31+G(3df,2p) and also a correlation consistent basis set, cc-pVTZ. It turns out that the selected basis set has a relatively finite influence on the calculated electronic transition energies as well as the topology of the absorption shape, but both are significantly affected by the chosen functional. In the present case, no single functional simultaneously provides highly accurate positions and intensities of the different bands, but mPW1PBE and mPW1LYP appear to be a good compromise. The mPW1PBE along with medium basis sets produced both absorption bands with maximum peaks about 463 and 346 nm. At all stages, ethanol has been chosen as a solvent environment. To improve the accuracy of first electronic excitation, a complete analysis of the origin of the band shape using TD-DFT vibrational couplings was performed. Finally the computed transition energy was corrected to 472 nm which was in excellent agreement with experiments.

show abstract

TD-DFT Vibronic Couplings in Anthraquinones: From Basis Set and Functional Benchmarks to Applications for Industrial Dyes

Cited by 128 publications

References 82 publications

The photochemistry of transition metal complexes using density functional theory

The photochemistry of transition metal complexes using density functional theory

Benchmarking Density Functionals on Structural Parameters of Small-/Medium-Sized Organic Molecules

Absorption of DCM Dye in Ethanol: Experimental and Time Dependent Density Functional Study

Contact Info

Product

Resources

About