Nonadiabatic Ensemble Simulations of <i>cis-</i>Stilbene and <i>cis</i>-Azobenzene Photoisomerization

Neukirch, Amanda; Shamberger, Logan C.; Abad, E.; Haycock, Barry; Hong, Wang; Ortega, José; Prezhdo, Oleg V.; Lewis, James P.

doi:10.1021/ct4009816

Cited by 55 publications

(61 citation statements)

References 75 publications

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“…A typical example of such a class is azobenzene, which has been studied with SH/ROKS [164] and SH/SDKS [165]. Dynamics based on both provides a good description of the cis-trans isomerization of azobenzene in the gas phase in comparison to other semiempirical and ab initio wavefunction-based surface hopping simulations [176][177][178][179][180].…”

Section: Case Studiesmentioning

confidence: 99%

Surface Hopping Dynamics with DFT Excited States

Barbatti

Crespo‐Otero

2014

Topics in Current Chemistry

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Nonadiabatic dynamics simulation of electronically-excited states has been a research area of fundamental importance, providing support for spectroscopy, explaining photoinduced processes, and predicting new phenomena in a variety of specialties, from basic physical-chemistry, through molecular biology, to materials engineering. The demands in the field, however, are quickly growing, and the development of surface hopping based on density functional theory (SH/DFT) has been a major advance in the field. In this contribution, the surface hopping approach, the methods for computation of excited states based on DFT, the connection between these methodologies, and their diverse implementations are reviewed. The shortcomings of the methods are critically addressed and a number of case studies from diverse fields are surveyed.

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Section: Case Studiesmentioning

confidence: 99%

Surface Hopping Dynamics with DFT Excited States

Barbatti

Crespo‐Otero

2014

Topics in Current Chemistry

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“…There are many examples of photochemical isomerisations to involve conical intersections, and cis-to-trans and trans-to-cis azobenzene photoisomerization as a prototype has been extensively studied, both theoretically [15][16][17][18][19][20][21][22] and experimentally [ref. 14 Conical intersections exhibit localized characterization of nonadiabatic transitions, such that simulated trajectory may make surface hopping mostly appear in the local region of avoided crossing zones.…”

Section: Introductionmentioning

confidence: 99%

Trajectory-based nonadiabatic molecular dynamics without calculating nonadiabatic coupling in the avoided crossing case: trans ↔ cis photoisomerization in azobenzene

Lei

et al. 2014

Phys. Chem. Chem. Phys.

131

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We develop a novel method to simulate analytical nonadiabatic switching probability based on effective coupling and effective collision energy by using only electronic adiabatic potential energy surfaces and its gradients in the case of avoided crossing types of nonadiabatic transitions. In addition, the present method can keep the same time step for computing both on-the-fly trajectory and nonadiabatic transitions accurately. The present method is most useful for localized nonadiabatic transitions induced by conical intersection. We employ the on-the-fly surface hopping algorithm with an ab initio quantum chemistry calculation to demonstrate a dynamic simulation for photoisomerization in azobenzene. Simulated quantum yield and lifetime converge to 0.39 and 53 femtosecond, respectively (0.33 and 0.81 picosecond) for cis-to-trans (trans-to-cis) photoisomerization with up to 800 (600) sampling trajectories. The present results agree well with those of the experiment, as well as results simulated with use of nonadiabatic coupling within Tully's fewest switching method. The present trajectory-based nonadiabatic molecular dynamics free from nonadiabatic coupling greatly enhances the simulation power of molecular dynamics for large complex chemical systems.

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“…[25,26] Angeli et al confirmedt hat the ordering obtained by using TD-DFT was accurate. [48] TD-DFT was also combined with nonadiabatic molecular dynamics simulations to investigate the photoisomerization of stilbene, [49,50,51] spin-flipT D-DFTw as used to pinpoint the conical intersection, [52] and vibronic couplings werea lso evaluated for trans stilbene. [53] Overall,acomprehensive description of the properties of stilbene in both its GS and ESs is therefore available.…”

Section: Introductionmentioning

confidence: 99%

A Joint Theoretical and Experimental Study of the Behavior of the DIDS Inhibitor and its Derivatives

et al. 2016

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4,4'-Diisothiocyanostilbene-2,2'-disulfonic acid (DIDS) is a well-known ion-exchange inhibitor targeting cardiac functions and indirectly impeding both radio- and chemo-resistance. A joint computational and experimental study is presented to provide deeper insights into DIDS and other members of this family of compounds. To this end, we applied state-of-the-art density functional theory (DFT) and time-dependent DFT methods, in addition to measuring the optical properties. The experimental data show that such compounds are highly sensitive to their environment and that the optical properties change within as little time as 7 h. However, the optical properties of DIDS are similar in various acidic/basic environments, which were confirmed by pKa computations on both cis and trans isomers. The protonation analysis also highlights that the singly protonated form of DIDS behaves like a proton sponge compound. The experimentally observed redshift that can be seen when going from water to DMSO was reproduced solely by using the solvation model based on density, although the polarization continuum model and implicit/explicit hybrid schemes were also tested. The characteristic broadening of the absorption peak in water and the vibronic fine structure in DMSO were also reproduced thanks to vibronic coupling simulations associated with the solvent reorganization energy. For other stilbene derivatives, a correlation is found between the maximum absorption wavelength and the Hammett parameters.

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Nonadiabatic Ensemble Simulations of cis-Stilbene and cis-Azobenzene Photoisomerization

Cited by 55 publications

References 75 publications

Surface Hopping Dynamics with DFT Excited States

Surface Hopping Dynamics with DFT Excited States

Trajectory-based nonadiabatic molecular dynamics without calculating nonadiabatic coupling in the avoided crossing case: trans ↔ cis photoisomerization in azobenzene

A Joint Theoretical and Experimental Study of the Behavior of the DIDS Inhibitor and its Derivatives

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