Performance of DFT functionals for calculating the second-order nonlinear optical properties of dipolar merocyanines

Lescos, Laurie; Sitkiewicz, Sebastian P.; Beaujean, Pierre; Blanchard‐Desce, Mireille; Champagne, Benoı̂t; Matito, Eduard; Castet, Frédéric

doi:10.1039/d0cp02992k

Cited by 72 publications

(54 citation statements)

References 57 publications

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“…Hence, a percentage of nearly 50% between DFT and HF exchange is the adequate balance for computing the NLO properties of these systems, as it was also concluded from previous works on smaller molecules 63 and conjugated push-pull chromophores. 64,65 These results thus contribute to the recent findings about the importance of the delocalization error in the calculation of linear and nonlinear optical properties. 64,[66][67][68][69] It is worth noticing that the recent strategy 69 of finding the optimal range-separation parameter to calculate from the values of ↵ works quite well to calculate the value of for these systems.…”

Section: Second-order Nlo Properties Reference Ab Initio Calculationssupporting

confidence: 69%

Impact of Van der Waals interactions on structural and nonlinear optical properties of azobenzene switches

Naim¹,

Castet²,

Matito

2021

Preprint

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<div> <div> <div> <p>The geometrical structures, relative Z-E energies, and second-order nonlinear responses of a collection of azobenzene molecules symmetrically substituted in meta- position with functional groups of different bulkiness are investigated using various ab initio and DFT levels of approximation. We show that RI-MP2 and RI-CC2 approximations provide very similar geometries and relative energies and evidence that London dispersion interactions existing between bulky meta-substituents stabilize the Z con- former. The !B97-X-D exchange-correlation functional provides an accurate description of these effects and gives a good account of the nonlinear optical response of the molecules. We show that density functional approximations should include no less than 50% of Hartree-Fock exchange to provide accurate hyperpolarizabilities. A property-structure analysis of the azobenzene derivatives reveals that the main contribution to the first hyperpolarizability comes from the azo bond, but phenyl meso-substituents can enhance it.</p> </div> </div> </div>

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Section: Second-order Nlo Properties Reference Ab Initio Calculationssupporting

confidence: 69%

Impact of Van der Waals interactions on structural and nonlinear optical properties of azobenzene switches

Naim¹,

Castet²,

Matito

2021

Preprint

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“…Different benchmark studies highlight the dependency of extended organic dyes’ NLO properties on the exchange-correlation functional and basis set. However, recent research has shown that range-separated hybrid functionals, such as CAM-B3LYP, are the best choice for the calculation of first order hyperpolarizabilities ( Garza et al, 2015 ; Lescos et al, 2020 ). For the particular case of Hückel and Möbius π -conjugation topologies, Torrent-Sucarrat et al showed that the hybrid M05-2X and the long-range corrected CAM-B3LYP provide a semi-quantitative description of the NLO properties at a reasonable computational cost ( Torrent-Sucarrat et al, 2011 ; Torrent-Sucarrat et al, 2012 ; Torrent-Sucarrat et al, 2017b ).…”

Section: Methodsmentioning

confidence: 99%

“…As such, the 6-311+G(d,p) basis set employed in our study is adequate to compute the β HRS values of the Hückel and Möbius conformers of hexaphyrins. Indeed, in a very recent benchmark study on the influence of the amount of exact Hartree–Fock exchange included in the DFT functional on the magnitude of the static HRS responses, a similar basis set 6-311+G(d) was employed ( Lescos et al, 2020 ).…”

Section: Methodsmentioning

confidence: 99%

Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design

et al. 2021

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In the search for new nonlinear optical (NLO) switching devices, expanded porphyrins have emerged as ideal candidates thanks to their tunable chemical and photophysical properties. Introducing meso-substituents to these macrocycles is a successful strategy to enhance the NLO contrasts. Despite its potential, the influence of meso-substitution on their structural and geometrical properties has been scarcely investigated. In this work, we pursue to grasp the underlying pivotal concepts for the fine-tuning of the NLO contrasts of hexaphyrin-based molecular switches, with a particular focus on the first hyperpolarizability related to the hyper-Rayleigh scattering (βHRS). Building further on these concepts, we also aim to develop a rational design protocol. Starting from the (un)substituted hexaphyrins with various π-conjugation topologies and redox states, structure-property relationships are established linking aromaticity, photophysical properties and βHRS responses. Ultimately, inverse molecular design using the best-first search algorithm is applied on the most favorable switches with the aim to further explore the combinatorial chemical compound space of meso-substituted hexaphyrins in search of high-contrast NLO switches. Two definitions of the figure-of-merit of the switch performance were used as target objectives in the optimization problem. Several meso-substitution patterns and their underlying characteristics are identified, uncovering molecular symmetry and the electronic nature of the substituents as the key players for fine-tuning the βHRS values and NLO contrasts of hexaphyrin-based switches.

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“…Generally speaking, the photophysical and nonlinear optical (NLO) properties of these chromophores can be controlled by adjusting their structural modules: electron donor, π-conjugated linker, or electron acceptor. [20][21][22][23][24] Since Baker and coworkers put forward the concept of "mesoionic" in 1949, 25,26 mesoionic rings defined by planar five-or six-membered heterocyclic betaines with at least one side-chain whose -atom in the ring plane have been recognized as a promising candidate for conjugated bridges of optical materials because of their electronic mobility. 27 Numerous mesoionic compounds with different electron donors and electron acceptors have been studied both theoretically and experimentally.…”

Section: Introductionmentioning

confidence: 99%

Effects of External Field Wavelength and Solvation on the Photophysical Property and Optical Nonlinearity of 1,3-Thiazolium-5-Thiolates Mesoionic Compound

Hua¹,

Liu²,

Tian³

2021

Preprint

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<p>The photophysical property and optical nonlinearity of an electronic push-pull mesoionic compond, 2-(4-trifluoromethophenyl)-3-methyl-4-(4-methoxyphenyl)-1,3-thiazole-5-thiolate were theoretically investigated with a reliable computing strategy. The essence of the optical properties were then explored through a variety of wave function analysis methods, such as the natural transition orbital analysis, hole-electron analysis, (hyper)polarizability density analysis, decomposition of the (hyper)polarizability contribution by numerical integration, and (hyper)polarizability tensor analysis, at the level of electronic structures. The influence of the electric field and solvation on the electron absorption spectra and (hyper)polarizabilities of the molecule are highlighted and clarified. This work will help people to understand the influence of external field wavelength and solvent on the optical properties of mesoionic-based molecules, and provide a theoretical reference for the rational design of chromophores with adjustable properties in the future.<br></p><br>

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Performance of DFT functionals for calculating the second-order nonlinear optical properties of dipolar merocyanines

Abstract:
The second-order nonlinear optical responses of a series of recently designed dipolar merocya- nines are investigated using the 2006 Minnesota family of hybrid exchange-correlation functionals (XCFs), as well as the...

Cited by 72 publications

References 57 publications

Impact of Van der Waals interactions on structural and nonlinear optical properties of azobenzene switches

Impact of Van der Waals interactions on structural and nonlinear optical properties of azobenzene switches

Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design

Effects of External Field Wavelength and Solvation on the Photophysical Property and Optical Nonlinearity of 1,3-Thiazolium-5-Thiolates Mesoionic Compound

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Performance of DFT functionals for calculating the second-order nonlinear optical properties of dipolar merocyanines

Abstract: The second-order nonlinear optical responses of a series of recently designed dipolar merocya- nines are investigated using the 2006 Minnesota family of hybrid exchange-correlation functionals (XCFs), as well as the...

Cited by 72 publications

References 57 publications

Impact of Van der Waals interactions on structural and nonlinear optical properties of azobenzene switches

Impact of Van der Waals interactions on structural and nonlinear optical properties of azobenzene switches

Fine-Tuning of Nonlinear Optical Contrasts of Hexaphyrin-Based Molecular Switches Using Inverse Design

Effects of External Field Wavelength and Solvation on the Photophysical Property and Optical Nonlinearity of 1,3-Thiazolium-5-Thiolates Mesoionic Compound

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Abstract:
The second-order nonlinear optical responses of a series of recently designed dipolar merocya- nines are investigated using the 2006 Minnesota family of hybrid exchange-correlation functionals (XCFs), as well as the...