Spectral broadening and red edge excitation effect in liquid and viscous solutions of DMABN

Томин, В. И.; Dubrovkin, J.; Włodarkiewicz, Agnieszka

doi:10.1016/j.jlumin.2017.05.074

Cited by 4 publications

(3 citation statements)

References 31 publications

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“…The TICT state theory, that claims that an internal rotation charge transfer state is responsible for the anomalous emission is the most accepted theory and has been supported by superjet cluster measurements [ 19 ], fragment orbital interaction and excited state energy decomposition analysis [ 20 ], by measurements in DMABN derivatives, the torsion of which was impeded sterically [ 21 ], by excitation to the red edge band [ 22 ] and by solvatochromic analysis of absorption and emission data [ 23 ].…”

Section: Introductionmentioning

confidence: 99%

Micro-Solvated DMABN: Excited State Quantum Dynamics and Dual Fluorescence Spectra

2021

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In this work, we report a complete analysis by theoretical and spectroscopic methods of the short-time behaviour of 4-(dimethylamino)benzonitrile (DMABN) in the gas phase as well as in cyclohexane, tetrahydrofuran, acetonitrile, and water solution, after excitation to the La state. The spectroscopic properties of DMABN were investigated experimentally using UV absorption and fluorescence emission spectroscopy. The computational study was developed at different electronic structure levels and using the Polarisable Continuum Model (PCM) and explicit solvent molecules to reproduce the solvent environment. Additionally, excited state quantum dynamics simulations in the diabatic picture using the direct dynamics variational multiconfigurational Gaussian (DD-vMCG) method were performed, the largest quantum dynamics “on-the-fly” simulations performed with this method until now. The comparison with fully converged multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) dynamics on parametrised linear vibronic coupling (LVC) potentials show very similar population decays and evolution of the nuclear wavepacket. The ring C=C stretching and three methyl tilting modes are identified as the responsible motions for the internal conversion from the La to the Lb states. No major differences are observed in the ultrafast initial decay in different solvents, but we show that this effect depends strongly on the level of electronic structure used.

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Section: Introductionmentioning

confidence: 99%

Micro-Solvated DMABN: Excited State Quantum Dynamics and Dual Fluorescence Spectra

2021

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“…We think that the extra component of band appear due to the bad fitting model based on symmetric Gaussian shapes. It is well known that the vibronic spectra of organic molecules have asymmetric shapes, namely, the emission spectral intensity increases slower in the region of the long wavelengths than in that of the short wavelength [2,12,14,[25][26][27]28]. The band asymmetry in the spectra of all compounds studied in the article is clearly observed in figures 2 and 3 presented in different x-scales, cm −1 and, respectively.…”

Section: Vladimir I Tominmentioning

confidence: 71%

“…asymmetric sigmoidal functions (see ORIGIN packages and [26,27]). Smart fitting procedures based on the asymmetric double sigmoid functions (ASIGM) allowed us significantly reduce fitting errors [27][28][29].…”

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confidence: 99%