Theoretical approaches for predicting the color of rigid dyes in solution

Abstract

Aiming at developing an affordable and easily implementable computational protocol for routine prediction of spectral properties of rigid molecular dyes, density functional theory, and time-dependent density functional theory were used in conjunction with a vibronic coupling scheme for band shape estimate. To predict the perceived color of molecules in solution, a model has been setup linking the UV-vis spectra predicted at ab initio level to the L*a*b* colorimetric parameters. The results show that a mixed protocol, implying the use of a global hybrid functional for the prediction of adiabatic energy differences and a range separated hybrid for the prediction of potential energy curvature, allows perceived colors to be quantitatively predicted, as demonstrated by the comparison of L*a*b* colorimetric parameters obtained from computed and experimental spectra. © 2017 Wiley Periodicals, Inc.

Triangulenium dyes: the comprehensive photo-absorption and emission story of a versatile family of chromophores

“…[44][45][46][47] Pushed by methodological investigations [48][49][50][51] and the concomitant implementation of the analytical TDDFT Hessian matrix, 52 it allowed to comprehensively understand the UV/vis absorption and emission signatures of several large organic and organometallic chromophores, [53][54][55] and to go beyond with the accurate simulation of intuitive parameters such as the perceived colors of dyes in solution. [56][57][58] In this investigation, we want to take advantage of the state-ofthe-art quantum chemistry toolbox to establish a robust computational protocol allowing a comprehensive understanding of the large and complex vibrationally-resolved photo-absorption and emission spectra of triangulenium dyes. More precisely, we want to show our interest in the rationalization of the UV/vis spectroscopic properties of the most popular core compounds of the triangulenium dyes, i.e.…”

A combined Monte Carlo/DFT approach to simulate UV‐vis spectra of molecules and aggregates: Merocyanine dyes as a case study

“…The flexible structure of merocyanines adds another level of complexity in the modeling. Indeed, standard methods to obtain the vibrationally resolved optical spectra 22–25 cannot be applied in this situation due to the presence of several energetically accessible minima existing on the ground and/or excited state potential energy surfaces (PESs) 26–28 . In such cases a single structure can hardly be representative of the real phase space and ensemble averages become mandatory.…”

Highly selective chromoionophores for ratiometric Na+sensing based on an oligoethyleneglycol bridged bithiophene detection unit

“…Although computational simulations with similar accuracies have been reported in the literature, these have been conducted for a well-known class of highly rigid dyes with similar molecular structures and absorption maxima lying within a wavelength range of less than 100 nm. 28 Moreover, these calculations also required the use of a mixed functional protocol to achieve such accuracy. To further highlight the potential of our computational model, we also predicted the S0S1 b transition of the bound sensor.…”