Benchmarking the Performance of Exchange-Correlation Functionals for Predicting Two-Photon Absorption Strengths

Beerepoot, Maarten T. P.; Alam, Md. Mehboob; Bednarska, Joanna; Bartkowiak, Wojciech; Ruud, Kenneth; Zaleśny, Robert

doi:10.1021/acs.jctc.8b00245

Cited by 72 publications

(114 citation statements)

References 70 publications

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“…The results of such comparisons performed for organic molecules demonstrate that two‐photon transition strengths are commonly underestimated by range‐separated functionals (LC‐BLYP, CAM‐B3LYP) and that global hybrid functionals (like B3LYP) are more successful in predicting the

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magnitude. However, as recently shown by some of us for a series of four‐coordinate organoboron N,C chelates, only range‐separated functionals correctly predict changes in

δ^{2 PA}

upon chemical modifications and reproduce experimental trends . In other words, global hybrids provide more accurate orders of magnitude for TPA cross‐sections, but less consistent chemical ranking.…”

Section: Resultsmentioning

confidence: 83%

“…1 allows to derive the expression for a generalized few‐state model for non‐Hermitian theories, where the left and right transition moments are different. The final expression for the 2PA strength is given by:

true δ_{0 J K L}^{GFSM} = \sum_{K} \sum_{L} \frac{2}{15 Δ E_{K} Δ E_{L}} (α + β), α = | μ^{J K} | | μ^{K 0} | | μ^{0 L} | | μ^{L J} | ({\cos θ}_{J K}^{K 0} {\cos θ}_{0 L}^{L J} + {\cos θ}_{J K}^{0 L} {\cos θ}_{K 0}^{L J} + {\cos θ}_{J K}^{L J} {\cos θ}_{K 0}^{0 L}) β = | μ^{J L} | | μ^{L 0} | | μ^{0 K} | | μ^{K J} | ({\cos θ}_{J L}^{L 0} {\cos θ}_{0 K}^{K J} + {\cos θ}_{J L}^{0 K} {\cos θ}_{L 0}^{K J} + {\cos θ}_{J L}^{K J} {\cos θ}_{L 0}^{0 K})

…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

“…More recent studies by Alam et al . contributed to the field by development of a generalized few‐state model (GFSM) for TPA, which was recently extended to coupled‐cluster method and further generalized to multiphoton absorption …”

Section: Introductionmentioning

confidence: 99%

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Design of Two‐Photon‐Excited Fluorescent Dyes Containing Fluoroborylene Groups

et al. 2019

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Aiming at establishing structure-property relationships for twophoton absorption, we present the results of an in silico investigation of dyes containing fluoroborylene (BF) groups. More specifically, we analyze the electronic properties corresponding to the one-and two-photon excitation to two lowestlying singlet states (S 1 and S 2 ) using TD-DFT and CC2 methods. BF-and BF 2 -containing fluorescent dyes are in the limelight, but it remains challenging to reach the larger electronic two-photon transition strengths needed in bioimaging applications. Hence, we put an emphasis on maximizing those strengths through structural variations. To this end, we consider 138 unique molecules deriving from five different structural cores present-ing BF/BF 2 groups. This molecular set encompasses representatives of three architectures, built with different arrangements of electron-donating (D) and electron-withdrawing (A) moieties: D-A, D-A-D and D-A-A-D. In addition, we consider several πconjugated linkers of different lengths, composed of ethylene (en) and 1,4-phenylene (PH) units (up to -enPHenPH-), and a panel of substituents (R = H, OMe, NMe 2 and NPh 2 ). For the twophoton transitions, it is shown that not only the linker extension and the strength of the electron-donating substituent are crucial for maximizing the two-photon activity but also the central core possessing fluoroborylene unit. The results have been rationalized by using a generalized three-level model.

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δ^{2 PA}

magnitude. However, as recently shown by some of us for a series of four‐coordinate organoboron N,C chelates, only range‐separated functionals correctly predict changes in

δ^{2 PA}

Section: Resultsmentioning

confidence: 83%

true δ_{0 J K L}^{GFSM} = \sum_{K} \sum_{L} \frac{2}{15 Δ E_{K} Δ E_{L}} (α + β), α = | μ^{J K} | | μ^{K 0} | | μ^{0 L} | | μ^{L J} | ({\cos θ}_{J K}^{K 0} {\cos θ}_{0 L}^{L J} + {\cos θ}_{J K}^{0 L} {\cos θ}_{K 0}^{L J} + {\cos θ}_{J K}^{L J} {\cos θ}_{K 0}^{0 L}) β = | μ^{J L} | | μ^{L 0} | | μ^{0 K} | | μ^{K J} | ({\cos θ}_{J L}^{L 0} {\cos θ}_{0 K}^{K J} + {\cos θ}_{J L}^{0 K} {\cos θ}_{L 0}^{K J} + {\cos θ}_{J L}^{K J} {\cos θ}_{L 0}^{0 K})

…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

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Design of Two‐Photon‐Excited Fluorescent Dyes Containing Fluoroborylene Groups

et al. 2019

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“…the effect of relative orientations of different transition dipole moment vectors. Since different transition dipole moment vectors are directly related to the structure of the molecule, this additional information allows few-state models to reveal important structure-property relationships [35,[56][57][58][59][60][61][62][63][64].…”

Section: Few-state Model Analysis Of Tpa In the H-g Complexesmentioning

confidence: 99%

Two-photon absorption in host-guest complexes

Alam

Ruud

2020

Molecular Physics

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We present an extensive analysis of one-and two-photon absorption processes in some organic hostguest (H-G) complexes using linear and quadratic response theory within the framework of timedependent density functional theory. For this purpose, we have considered all possible 20 host-guest complexes constructed from 4 host and 5 guest molecules. We have analysed how the one-and two-photon activity of the host and guest molecules are transferred to the respective host-guest complexes and how the electron donating and electron accepting ability of host-guest complexes affect their two-photon activity. Based on an analysis using the concept of channel interference, we have performed an in-depth analysis of the two-photon absorption processes in all these systems and provided a microscopic explanation for their variation among different complexes.

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“…In order to analyze the two-photon activity, we have employed the generalized few-state model (GFSM) 40 recently developed for electronic structure theories with a nonhermitian structure. 41 GFSM allows to interpret the two-photon transition strengths in terms of electronic structure parameters: where …”

mentioning

confidence: 99%

Controlling Two-Photon Action Cross Section by Changing a Single Heteroatom Position in Fluorescent Dyes

Ośmiałowski

Petrusevich

Antoniak

et al. 2020

J. Phys. Chem. Lett.

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The optimization of nonlinear optical properties for “real-life” applications remains a key challenge for both experimental and theoretical approaches. In particular, for two-photon processes, maximizing the two-photon action cross section (TPACS), the figure of merit for two-photon bioimaging spectroscopy, requires simultaneously controlling all its components. In the present Letter, a series of difluoroborates presenting various heterocyclic rings as an electron acceptor have been synthesized and their absorption, fluorescence, photoisomerization, and two-photon absorption features have been analyzed using both experimental and theoretical approaches. Our results demonstrate that the TPACS values can be fine-tuned by changing the position of a single heteroatom, which alters the fluorescence quantum yields without changing the intrinsic two-photon absorption cross section. This approach offers a new strategy for optimizing TPACS.

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Benchmarking the Performance of Exchange-Correlation Functionals for Predicting Two-Photon Absorption Strengths

Cited by 72 publications

References 70 publications

Design of Two‐Photon‐Excited Fluorescent Dyes Containing Fluoroborylene Groups

Design of Two‐Photon‐Excited Fluorescent Dyes Containing Fluoroborylene Groups

Two-photon absorption in host-guest complexes

Controlling Two-Photon Action Cross Section by Changing a Single Heteroatom Position in Fluorescent Dyes

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