Electronic-structure and quantum dynamical study of the photochromism of the aromatic Schiff base salicylideneaniline

Ortiz-Sánchez, Juan Manuel; Gelabert, Ricard; Moreno, Miquel; Lluch, José M.

doi:10.1063/1.3032215

Cited by 97 publications

(170 citation statements)

References 71 publications

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“…This twist coordinate was previously found to be the relaxation path competing with ESIPT. 17,28 3.2. Absorption Spectra.…”

Section: Resultsmentioning

confidence: 99%

“…In the ground state, the molecule is twisted by 35°about the anil group. geometry in S 1 given by Ortiz-Sańchez et al, 28 were also calculated. For the twisted geometries, we manually rotated the anilino group and optimized the structures with a fixed dihedral angle in the ground state.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

“…9,[14][15][16][17]22,24,28,29 Theory predicts a ground-state torsion angle of 36°about the anil twist angle α (C 7 NC 6 C 5 dihedral angle; see Figure 1c for a definition of the critical angles considered in this study) at the B3LYP/6-31G* level of theory 28 and 44°at the HF/6-31G* level. 29 An angle of 49°was found by X-ray diffraction of crystalline SA.…”

Section: Introductionmentioning

confidence: 91%

“…This path might proceed through an intermediate nπ* state, 29 although more recent work predicts a direct conversion to the ground state through a conical intersection (CI). 28 The conversion rate of this process is claimed to be on the order of that of ESIPT, rendering it a competing process. 28,29 Most experimental results can be understood in terms of this picture.…”

Section: Introductionmentioning

confidence: 99%

“…28 The conversion rate of this process is claimed to be on the order of that of ESIPT, rendering it a competing process. 28,29 Most experimental results can be understood in terms of this picture. 9,[15][16][17]24,32 For example, REMPI experiments showed a relaxation of the S 1 state of the enol form within less than a few hundred femtoseconds, 24 which was explained by the two processes taking place in parallel.…”

Section: Introductionmentioning

confidence: 99%

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Initial Processes of Proton Transfer in Salicylideneaniline Studied by Time-Resolved Photoelectron Spectroscopy

Sekikawa

Schalk

et al. 2013

J. Phys. Chem. A

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Excited-state intramolecular proton transfer (ESIPT) in salicylideneaniline (SA) and selected derivatives substituted in the para position of the anilino group have been investigated by femtosecond time-resolved photoelectron spectroscopy (TRPES) and time-dependent density functional theory (TDDFT). SA has a twisted structure at the energetic minimum of the ground state, but ESIPT is assumed to take place through a planar structure, although this has not been fully established. The TRPES studies revealed that the excited-state dynamics within the S 1 band varied significantly with excitation wavelength. At finite temperatures, the ground state was found to sample a broad range of torsional angles, from planar to twisted. At lower photon energies (370 nm), only the planar groundstate molecules were excited, and the excited-state reaction took place within 50 fs. At higher energies (350 and 330 nm), predominantly twisted ground-state molecules were excited: they had to planarize before ESIPT could occur. This process was found to be slower in methylated SA but did not change significantly in the brominated and nitrated SAs. These substitution effects on the decay dynamics can be explained by modifications of the potential barriers, as predicted by the TDDFT calculations, and support the mechanism of a twisting motion of the anilino ring prior to ESIPT. The contribution of another pathway leading to internal conversion within the enol form was found to be minor at the excitation wavelengths considered here.

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“…This twist coordinate was previously found to be the relaxation path competing with ESIPT. 17,28 3.2. Absorption Spectra.…”

Section: Resultsmentioning

confidence: 99%

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Initial Processes of Proton Transfer in Salicylideneaniline Studied by Time-Resolved Photoelectron Spectroscopy

Sekikawa

Schalk

et al. 2013

J. Phys. Chem. A

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Deconvolution of femtosecond time‐resolved spectroscopy data in multivariate curve resolution. Application to the characterization of ultrafast photo‐induced intramolecular proton transfer

Mouton

Sliwa

Buntinx

et al. 2010

Journal of Chemometrics

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In femtosecond absorption spectroscopy, deconvolution of the measured kinetic traces is still an important issue as photochemical processes that may possess shorter characteristic times than the time resolution of the experiment are usually considered. In this work, we propose to perform deconvolution of the time-dependent concentration profiles extracted from multivariate curve resolution (MCR) applied to spectrokinetic data. The profiles are fitted with a model function including a description of the instrumental response function (IRF) of the experiment. The method combines the potential benefits of soft-modeling data analysis with the ones of hard-modeling for parameter estimation. The potential of the method is demonstrated first analyzing five synthetic data sets for which IRF of different widths are simulated. It is then successfully applied to resolve femtosecond UV-visible transient absorption spectroscopy data investigating the photodynamics of salicylidene aniline, a photochromic molecule of wide interest. Considering a time resolution of 150 fs for the IRF, a characteristic time of 45 fs is recovered for the first step of the photo-induced process which consists of an ultrafast intramolecular proton transfer. Our results also confirm the existence of an intermediate species with a characteristic time of 240 fs.

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Bipyridyl Derivatives as Photomemory Devices: A Comparative Electronic‐Structure Study

Ortiz-Sánchez

Gelabert

Moreno

et al. 2010

Chemistry A European J

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The two isoelectronic bipyridyl derivatives [2,2'-bipyridyl]-3,3'-diamine (BP(NH(2))(2)) and [2,2'-bipyridyl]-3,3'-diol (BP(OH)(2)) are experimentally known to undergo very different excited-state double proton transfer processes that result in fluorescence quantum yields that differ by four orders of magnitude. Such differences have been theoretically explained in terms of topographical features in the potential energy surface and the likely presence of conical intersections. The hypothetical hybrid compound [2,2'-bipyridyl]-3-amin-3'-ol (BP(OH)(NH(2))) presents intermediate photochemical features of its "ancestors". In this report we analyze the photochemical properties of a whole family of "dark" (not fluorescent) states that can be accessed from each bipyridyl derivative upon irradiation of light of a given wavelength and their potential application as photomemory devices. In the light of our density functional theory (DFT), time-dependent DFT (TDDFT), and complete active space self-consistent field (CASSCF) calculations, BP(NH(2))(2) is the more likely candidate to become a photomemory device.

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Electronic-structure and quantum dynamical study of the photochromism of the aromatic Schiff base salicylideneaniline

Cited by 97 publications

References 71 publications

Initial Processes of Proton Transfer in Salicylideneaniline Studied by Time-Resolved Photoelectron Spectroscopy

Initial Processes of Proton Transfer in Salicylideneaniline Studied by Time-Resolved Photoelectron Spectroscopy

Deconvolution of femtosecond time‐resolved spectroscopy data in multivariate curve resolution. Application to the characterization of ultrafast photo‐induced intramolecular proton transfer

Bipyridyl Derivatives as Photomemory Devices: A Comparative Electronic‐Structure Study

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