Can Diarylethene Photochromism Be Explained by a Reaction Path Alone? A CASSCF Study with Model MMVB Dynamics

Boggio‐Pasqua, Martial; Ravaglia, Marcella; Bearpark, Michael J.; Garavelli, Marco; Robb, Michael A.

doi:10.1021/jp036862e

Cited by 175 publications

(259 citation statements)

References 51 publications

Supporting

Mentioning

230

Contrasting

Unclassified

Order By: Relevance

“…The photochemistry of dithienylethene upon one-photon irradiation was studied in Ref. [9] using a molecular mechanics-valence bond computation. Dynamics was simulated on a hydrocarbon model system having the same potential energy surface topology as dithienylethene.…”

Section: Benchmark Study Of Dithienylethenementioning

confidence: 99%

“…Unlike thermally activated chemical reactions, which take place in the ground electronic state (S0), a photochemical process involves the electronically excited state (S1). During this process the reactive system is electronically excited from S0 to S1, and after some evolution on the upper potential energy surface (PES) decays back to the ground state in either product or reactant basin through conical intersections (CIX) [9].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Theory and computations of two-photon absorbing photochromic chromophores

Masunov

Михайлов

2010

Eur. J. Chem.

View full text Add to dashboard Cite

KEYWORDSExponential growth in information technology generates ever increasing amounts of data, making recording density of the storage media crucially important. Two-photon absorption was proposed as a basis for high-density multi-layer technology for optical memory and logic devices. This technology suggests to use polymers, doped with photochromic compounds that undergo a reversible photoinduced isomerization, or photoswitching. In this review we consider recent theoretical works and benchmarking studies of the DFT-based methods, capable to predict two-photon absorption (2PA) and photochemical activity, Next we review the applications of these methods to design a prototype molecule that combines the photonmode recording property of photochromic compounds with large 2PA cross-section. We conclude that a posteriori Tamm-Dancoff approximation to the second order CEO approach in Density Functional Theory is the powerful tool for both quantitative predictions and qualitative understanding of the excited state processes in photophysics and photochemistry. We also emphasize general principles for the rational design of a two-photon operated photoswitch.TDDFT Organic photochemistry Photocyclization Photoinduced reactions Two-photon absorption State-to-state transition dipoles

show abstract

Section: Benchmark Study Of Dithienylethenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theory and computations of two-photon absorbing photochromic chromophores

Masunov

Михайлов

2010

Eur. J. Chem.

View full text Add to dashboard Cite

show abstract

“…In the many examples we have studied to date, we have usually been able to infer that these optimized conical intersection points are minima in the intersection space ͑IS͒, but until now we have not been able to prove this by doing a frequency calculation, in the way that one can for a single Born-Oppenheimer surface. Now that on-the-fly dynamics is possible, [9][10][11][12][13] computations are beginning to explore the nature of the intersection hyperline away from its minimum and show that these higher-energy regions of a conical intersection hyperline can be chemically significant. Furthermore, algorithms have been developed to map out ͑minimum-energy path͒ segments of the hyperline explicitly.…”

Section: Introductionmentioning

confidence: 99%

The curvature of the conical intersection seam: An approximate second-order analysis

Paterson

Bearpark

Robb

et al. 2004

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

We present a method for analyzing the curvature ͑second derivatives͒ of the conical intersection hyperline at an optimized critical point. Our method uses the projected Hessians of the degenerate states after elimination of the two branching space coordinates, and is equivalent to a frequency calculation on a single Born-Oppenheimer potential-energy surface. Based on the projected Hessians, we develop an equation for the energy as a function of a set of curvilinear coordinates where the degeneracy is preserved to second order ͑i.e., the conical intersection hyperline͒. The curvature of the potential-energy surface in these coordinates is the curvature of the conical intersection hyperline itself, and thus determines whether one has a minimum or saddle point on the hyperline. The equation used to classify optimized conical intersection points depends in a simple way on the first-and second-order degeneracy splittings calculated at these points. As an example, for fulvene, we show that the two optimized conical intersection points of C 2v symmetry are saddle points on the intersection hyperline. Accordingly, there are further intersection points of lower energy, and one of C 2 symmetry-presented here for the first time-is found to be the global minimum in the intersection space.

show abstract

“…We invoked ab initio MO studies 42,43 and molecular dynamics calculations 44 of cis-1,2-(3,3′-dithienyl)ethylene as a model for the diarylethene family, and a qualitative representation of the potential energy surfaces (PES) is given in Scheme 3. The ground state PES presents two local minima corresponding to the open and closed isomers.…”

Section: Resultsmentioning

confidence: 99%

Photoswitchable fluorescent diheteroarylethenes: substituent effects on photochromic and solvatochromic properties

Gillanders

Giordano

Dı́az

et al. 2014

Photochem Photobiol Sci

View full text Add to dashboard Cite

Photoswitchable fluorescent diheteroarylethenes are promising candidates for applications in superresolution molecular localization fluorescence microscopy thanks to their high quantum yields and fatigue-resistant photoswitching characteristics. We have studied the effect of varying substituents on the photophysical properties of six sulfone derivatives of diheteroarylethenes, which display fluorescence in one (closed form) of two thermally stable photochromic states. Electron-donating substituents displace the absorption and emission spectra towards the red without substantially affecting the fluorescence quantum yields. Furthermore, ethoxybromo, a very electron-donating substituent, stabilizes the excited state of the closed isomer to the extent of almost entirely inhibiting its cycloreversion. Multi-parameter Hammett correlations indicate a relationship between the emission maxima and electron-donating character, providing a useful tool in the design of future photochromic molecules. Most of the synthesized compounds exhibit small bathochromic shifts and shorter fluorescence lifetimes with an increase in solvent polarity. However, the ethoxybromo-substituted fluorescent photochrome is unique in its strong solvatochromic behaviour, constituting a photoactivatable ( photochromic), fluorescent and highly solvatochromic small organic compound. The Catalán formalism identified solvent dipolarity as the principal basis of the solvatochromism, reflecting the highly polarized nature of this molecule.

show abstract

Can Diarylethene Photochromism Be Explained by a Reaction Path Alone? A CASSCF Study with Model MMVB Dynamics

Cited by 175 publications

References 51 publications

Theory and computations of two-photon absorbing photochromic chromophores

Theory and computations of two-photon absorbing photochromic chromophores

The curvature of the conical intersection seam: An approximate second-order analysis

Photoswitchable fluorescent diheteroarylethenes: substituent effects on photochromic and solvatochromic properties

Contact Info

Product

Resources

About