Comparison of TD-DFT Methods for the Calculation of Two-Photon Absorption Spectra of Oligophenylvinylenes

Nayyar, Iffat; Masunov, Artëm E.; Tretiak, Sergei

doi:10.1021/jp403981d

Cited by 70 publications

(94 citation statements)

References 101 publications

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“…The specific choice of the damping constant X0 and the lorentzian line shape function Y 0 was used in the previous TD-DFT study. 31 linewidth value has been suggested as the best fit in earlier experimental 12 33 34 and theoretical 13 studies. Over the last decades, various theoretical approaches have been applied to the prediction as well as the interpretation of experimental measurements of NLO properties of the -conjugated organic molecules.…”

Section: Theorymentioning

confidence: 78%

“…For comparison of different semiempirical WFT methods and the previously calculated TD-DFT results, 31 we compare the root mean square deviation (RMSD) of the 1PA and 2PA predictions from the experimental data. 12 33 34 RMSD is a predictive measure of the differences between calculated (x 1 ) and experimentally observed (x 2 ) values given as…”

Section: Resultsmentioning

confidence: 99%

“…[31]. However, semiempirical methods are much faster and may be an attractive alternative for use in for the virtual high throughput screening for NLO material design.…”

Section: Computational Detailsmentioning

confidence: 99%

“…In this paper, we apply correlated semiempirical methods to a benchmark set of molecules shown on Figure 1 and compare the results to the experiment 12 33 34 and the previously calculated DFT predictions. 31 We use two types of semiempirical parameterizations: the "general purpose" PM6 and the "spectroscopic" ZINDO/S. …”

Section: Computational Detailsmentioning

confidence: 99%

“…[26][27][28][29][30] On the other hand, full coupled electronic oscillator formalism in the third order was applied at the DFT level to predict 2PA cross-sections in a benchmark set of olygophenylvinylenes. 31 Here we report on the accuracy of the semiempirical wavefunction theory predictions using the same benchmark set.…”

Section: Introductionmentioning

confidence: 99%

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Two-Photon Absorption Spectra Predicted by Semiempirical Methods

Nayyar¹,

Masunov²

2014

Jnl of Comp & Theo Nano

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The molecular markers with large two-photon absorption cross-sections are highly sought for many applications, from photodynamic therapy to optical information processing. One may envision computational design of the chromophores combining desirable one-and two-photon absorption (1PA and 2PA) optical features with other properties important for the specific applications (solubility, toxicity etc.). Semiempirical methods are fast and seem to be well suited for the high throughput computational screening, which may be a part of such rational design strategy. Here we apply several semiempirical methods for prediction of 2PA spectra for substituted olygophenylvinylenes of donor-acceptor type. The predictions are compared to the experiment and previously reported results of the density functional theory (DFT) methods. We find ZINDO/S spectroscopic parameterization combined with single configuration interaction (CIS) method to perform far superior to the general purpose PM6 parameterization combined with various CI schemes. The poor performance in the prediction of 2PA cross-sections at PM6 level is traced to inaccurate excitation energies and incorrect transition dipoles between the 1PA and 2PA states. The state-to-state transition dipoles predicted by the ZINDO/S method are much better, as 2PA cross-sections reach the accuracy comparable to TD-DFT predictions after empirical corrections to the excitation energies. We conclude that semiempirical parameterizations can be used only for qualitative analysis of the 2PA properties. The excitation energies are in need of empirical correction, such as QSPR a linear regression for specific class of molecules. The ZINDO/S parameterization combined with multi-reference CI schemes (such as MR-CIS) could yield a good description of the intensities of 1PA and 2PA excitations, provided the right selection in reference configurations, order of excitation and active space. It can not be considered a black-box method, which makes it unsuitable choice for the high throughput screening technique.

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Section: Theorymentioning

confidence: 78%

Section: Resultsmentioning

confidence: 99%

“…[31]. However, semiempirical methods are much faster and may be an attractive alternative for use in for the virtual high throughput screening for NLO material design.…”

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Two-Photon Absorption Spectra Predicted by Semiempirical Methods

Nayyar¹,

Masunov²

2014

Jnl of Comp & Theo Nano

Self Cite

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Pyrrolo[3,2‐b]pyrroles—From Unprecedented Solvatofluorochromism to Two‐Photon Absorption

Friese

Mikhaylov

Krzeszewski

et al. 2015

Chemistry A European J

114

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A combined experimental and theoretical study of the two-photon absorption properties of a series of quadrupolar molecules possessing a highly electron-rich heterocyclic core, pyrrolo[3,2-b]pyrrole is presented. In agreement with quantum-chemical calculations, we observe large two-photon absorption (2PA) cross-section values, σ2PA ~ 102–103 GM (1GM = 1050 cm4 s photon−1) at wavelengths 650–700 nm, corresponding to the 2-photon allowed but 1-photon forbidden transitions. The calculations also predict that increased planarity of this molecule via removal of two N-substituents leads to further increase in the σ2PA values. Surprisingly, the most quadrupolar pyrrolo[3,2-b]pyrrole derivative bearing two 4-nitrophenyl substituents at positions 2 and 5 demonstrates very strong solvatofluorochromic effect, with the fluorescence quantum yield as high as 0.96 in cyclohexane, while the fluorescence vanishes in DMSO.

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Catalytic‐Type Excited‐State N−H Proton‐Transfer Reaction in 7‐Aminoquinoline and Its Derivatives

Chang

Liu

et al. 2019

Chemistry A European J

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7‐Aminoquinoline (7AQ) and various amino derivatives thereof (‐NHR) have been strategically designed and synthesized to study their excited‐state proton‐transfer (ESPT) properties. Due to the large separation between the proton donor ‐NHR and the acceptor ‐N‐ site, ESPT in 7AQ derivatives, if available, should proceed under protic solvent catalysis. ESPT is found to be influenced by the acidity of ‐NHR and the basicity of the proton‐acceptor ‐N‐ in the quinoline moiety. The latter is varied by the resonance effect at the quinoline ‐N‐ site induced by the ‐NHR substituent. For those 7AQ derivatives undergoing ESPT, increased quinoline basicity results in a faster rate of ESPT, implying that proton donation from methanol to the quinoline moiety may serve as a key step in the process. Our studies also indicate the existence of an equilibrium between cis and trans arrangements of ‐NHR in terms of its hydrogen‐bond (H‐bond) configuration with methanol, whereby only the cis‐H‐bonded form undergoes methanol‐assisted ESPT. With one exception, the interconversion between cis and trans configurations is much faster than the rate of ESPT, yielding amino‐type (normal form) and imine‐type (proton‐transfer tautomer) emissions with distinct relaxation dynamics.

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Comparison of TD-DFT Methods for the Calculation of Two-Photon Absorption Spectra of Oligophenylvinylenes

Cited by 70 publications

References 101 publications

Two-Photon Absorption Spectra Predicted by Semiempirical Methods

Two-Photon Absorption Spectra Predicted by Semiempirical Methods

Pyrrolo[3,2‐b]pyrroles—From Unprecedented Solvatofluorochromism to Two‐Photon Absorption

Catalytic‐Type Excited‐State N−H Proton‐Transfer Reaction in 7‐Aminoquinoline and Its Derivatives

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