Theoretical Photochemistry of the Photochromic Molecules Based on Density Functional Theory Methods

Михайлов, И. В.; Masunov, Artëm E.

doi:10.1007/978-3-642-01973-9_19

Cited by 5 publications

(5 citation statements)

References 36 publications

(35 reference statements)

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“…The optical properties of isolated photochromic systems have been thoroughly explored with a range of quantum chemical methods. [242][243][244][245] It is necessary to locate conical intersections 246 when probing photochromic reaction pathways and hence methods able to simultaneously treat multiple electronic states should be employed. However, multiphotochromic compounds represent extended conjugated systems and contain too many ''active'' electrons to be treated with multi-configurational methods, such as the Complete Active Space Self-Consistent Field (CASSCF) method.…”

Section: Overviewmentioning

confidence: 99%

Multiphotochromic molecular systems

et al. 2015

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Molecular systems encompassing more than one photochromic entity can be used to build highly functional materials, thanks to their potential multi-addressability and/or multi-response properties. Over the last decade, the synthesis and spectroscopic and kinetic characterisation as well as the modeling of a wide range of multiphotochromes have been achieved in a field that is emerging as a distinct branch of photochemistry. In this review, we provide an overview of the available multiphotochromic compounds which use a variety of photoactive building blocks, e.g., diarylethene, azobenzene, spiropyran, naphthopyran or fulgimide derivatives. Their efficiency in terms of multi-responsiveness is discussed and several strategies to circumvent the most common limitation (i.e., the loss of photochromism of one part) are described.

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Section: Overviewmentioning

confidence: 99%

Multiphotochromic molecular systems

et al. 2015

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“…Experimental data are taken from (a) [140], (b) [137], (c) [152]. [160], where ATDA-UDFT produced the accurate energies for the HOMO-LUMO double excited state in the entire range of the bond breaking reaction coordinate C1…C6 for some benchmark molecular photoswitches, provided that the molecular geometry corresponds to that state. Since analytical gradients in the ATDA-UDFT approach are not yet implemented in the computer codes, the studies reviewd below use an approximation called Slater transition state (STS) method to optimize geometry of the excited states.…”

Section: Theorymentioning

confidence: 99%

“…Studies [30] and [160] used the Gaussian 2003 Rev. E1 suite of programs [112], and hybrid meta-GGA exchangecorrelation functional M05-2X from Truhlar's group [165].…”

Section: Compoundmentioning

confidence: 99%

Theory and computations of two-photon absorbing photochromic chromophores

Masunov

Михайлов

2010

Eur. J. Chem.

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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

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“…Potential energy surfaces were calculated using the Gaussian09 suite 33 following the ideas of Masunov and co-workers. 35,36 The def-SVP basis set was used with the PBE0 functional. To account for the diradical character near the transition state, the PES for the ground state was calculated using unrestricted DFT with broken symmetry guess, i.e., keyword guess = (mix, always) was used in Gaussian.…”

Section: B Theorymentioning

confidence: 99%

Optical spectrum, perceived color, refractive index, and non-adiabatic dynamics of the photochromic diarylethene CMTE

Wiebeler

Bader

Meier

et al. 2014

Phys. Chem. Chem. Phys.

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Photochromism allows for reversible light-induced conversion of a molecular species into a different form with significantly altered optical properties. One promising compound that excels with high fatigue resistance and shows its photochromic functionality both in solution and in molecular solid films is the diarylethene derivative CMTE. Here we present a comprehensive study of its photophysical properties with density-functional theory based methods and benchmark the results against higher-level quantum-chemical approaches and experiments. In addition to static properties such as optical absorption, perceived color, and refractive index, we also investigate reaction dynamics based on non-adiabatic ab initio molecular dynamics. This gives detailed insight into the molecules' ultrafast reaction dynamics and enables us to extract reaction time scales and quantum yields for the observed electrocyclic reaction following photoexcitation.

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Theoretical Photochemistry of the Photochromic Molecules Based on Density Functional Theory Methods

Cited by 5 publications

References 36 publications

Multiphotochromic molecular systems

Multiphotochromic molecular systems

Theory and computations of two-photon absorbing photochromic chromophores

Optical spectrum, perceived color, refractive index, and non-adiabatic dynamics of the photochromic diarylethene CMTE

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