Two‐Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two‐Photon Absorption Spectrum of Reichardt’s Dye

Wielgus, Małgorzata; Zaleśny, Robert; Murugan, N.; Kongsted, Jacob; Ågren, Hans; Samoć, Marek; Bartkowiak, Wojciech

doi:10.1002/cphc.201300695

Cited by 36 publications

(40 citation statements)

References 143 publications

(389 reference statements)

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“…[14][15][16][17][18][19][20][21][22][23] In fact, electronic structure calculations and related few-state model analyses frequently support experimental studies. 14,24,25 The majority of computational studies are undertaken to understand the relation between chemical/electronic structure and 2PA activity and this has become an important ingredient in material design. However, the success of the predictions obtained by computer simulations depends heavily on the accuracy of the electronic structure methods used.…”

Section: Introductionmentioning

confidence: 99%

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

Beerepoot

Alam

Bednarska

et al. 2018

J. Chem. Theory Comput.

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The present work investigates the performance of exchange-correlation functionals in the prediction of two-photon absorption (2PA) strengths. For this purpose, we considered six common functionals used for studying 2PA processes and tested these on six organoboron chelates. The set consisted of two semilocal (PBE and BLYP), two hybrid (B3LYP and PBE0), and two range-separated (LC-BLYP and CAM-B3LYP) functionals. The RI-CC2 method was chosen as a reference level and was found to give results consistent with the experimental data that are available for three of the molecules considered. Of the six exchange-correlation functionals studied, only the range-separated functionals predict an ordering of the 2PA strengths that is consistent with experimental and RI-CC2 results. Even though the range-separated functionals predict correct relative trends, the absolute values for the 2PA strengths are underestimated by a factor of 2-6 for the molecules considered. An in-depth analysis, on the basis of the derived generalized few-state model expression for the 2PA strength for a coupled-cluster wave function, reveals that the problem with these functionals can be linked to underestimated excited-state dipole moments and, to a lesser extent, overestimated excitation energies. The semilocal and hybrid functionals exhibit less predictable errors and a variation in the 2PA strengths in disagreement with the reference results. The semilocal and hybrid functionals show smaller average errors than the range-separated functionals, but our analysis reveals that this is due to fortuitous error cancellation between excitation energies and the transition dipole moments. Our results constitute a warning against using currently available exchange-correlation functionals in the prediction of 2PA strengths and highlight the need for functionals that correctly describe the electron density of excited electronic states.

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Section: Introductionmentioning

confidence: 99%

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

Beerepoot

Alam

Bednarska

et al. 2018

J. Chem. Theory Comput.

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“…This is consistent with the general observations that the donor-p-acceptor systems show larger TPA activity in moderately polar solvents as compared with that in very high or very low-polarity solvents. [38][39][40] The trend of d…”

Section: View Article Onlinementioning

confidence: 99%

Interplay of twist angle and solvents with two-photon optical channel interference in aryl-substituted BODIPY dyes

Alam

Misra

Ruud

2017

Phys. Chem. Chem. Phys.

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a Channel interference plays a crucial role in understanding the physics behind multiphoton absorption processes. In this work, we study the role of channel interference and solvent effects on the two-photon absorption in aryl-substituted boron dipyrromethene (BODIPY) dyes, a class of intramolecular charge-transfer (ICT) molecules. For this purpose, we consider fourteen dyes of this class with various donor/acceptor substitutions at the para position of the phenyl ring and with or without methyl (-CH 3 ) substitution on the BODIPY moiety. The presence of a methyl group on the BODIPY moiety affects the dihedral angle significantly, which in turn affects the one-(OPA) and two-photon absorption (TPA) properties of the molecules.Among the molecules studied, the one having the strong electron-donating dimethylamino group and no methyl substitution at the BODIPY moiety is found to have the highest TPA cross section. Our few-state model analysis shows that the large TPA activity of this molecule is due to the all positive contributions from different channel interference terms. Change in dielectric constant of the medium is found to have a profound impact on both the magnitude and sign of the channel interference terms. The magnitude of destructive channel interference gradually decreases with decreasing solvent polarity and becomes constructive in a low-polarity solvent. We also study the effect of rotating the phenyl ring with respect to the BODIPY moiety on the TPA activity. In the gas phase and in different solvents, we found that channel interference is changed from destructive to constructive on twisting the molecule. These results are explained by considering different dipole-, energy-and angle-terms appearing in the expression of a two-state model.

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“…Some recent studies have focused on describing the solvation of stilbazolium merocyanine [36][37][38], dimethylamino-nitro stilbene [39] and Reichardt's dye (2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio)phenolate) [40] in both polar and non-polar solvents. These compounds are zwitter ionic species which renders the spectral properties susceptible to change in the solvent polarity, which was also reproduced in the QM/MM calculations.…”

Section: Introductionmentioning

confidence: 99%

Optical properties of pyridine and methyl-pyridinium in water using DFT/MM

Nielsen¹,

Mikkelsen

2015

Molecular Physics

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Molecular properties such as excitation energies, polarisabilities and two-photon absorption cross-sections of pyridine and N-methyl-pyridinium embedded in a solvent of water are studied using density functional theory/molecular mechanics (DFT/MM) calculations. The purpose of this study is to study how well the differences between a cationic and a neutral specie can be predicted with water as the solvent. In order to answer this question, the DFT/MM method used is benchmarked in terms of convergence profiles, e.g. how many calculations are needed in order to obtain a statistically converged result. Quantification of for example how many water molecules needs to be included in the quantum mechanics system in the calculations before a converged molecular property is obtained which is also benchmarked. The latter will serve as valuable information in further calculations of larger organic molecules, where more experimental data are available. In this work, the calculated excitation energies are compared to experimentally determined ultraviolet/visible (UV/VIS) spectra of both pyridine and N-methyl-pyridinium and a reasonable agreement is found.

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Two‐Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two‐Photon Absorption Spectrum of Reichardt’s Dye

Cited by 36 publications

References 143 publications

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

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

Interplay of twist angle and solvents with two-photon optical channel interference in aryl-substituted BODIPY dyes

Optical properties of pyridine and methyl-pyridinium in water using DFT/MM

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