Azomethane: Nonadiabatic Photodynamical Simulations in Solution

Ruckenbauer, Matthias; Barbatti, Mario; Sellner, Bernhard; Müller, Thomas; Lischka, Hans

doi:10.1021/jp108844g

Cited by 52 publications

(53 citation statements)

References 43 publications

(87 reference statements)

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“…In spite of the fact that previous studies of the dynamics of the production of bathoRh from Rh 15,19,20 and of the isomerization dynamics of isolated or solvated retinal chromophore models [21][22][23][24][25] have appeared in the literature, we are unaware of any reported trajectory computation employing models where the entire chromophore is treated using ab initio quantum chemistry and where a full configuration interaction treatment is applied to the entire π-system. In the present work, Rh and bathoRh quantum-mechanics/ molecular-mechanics (QM/MM) models based on an ab initio multiconfigurational wave functions are employed to look at the light induced π-bond breaking and reconstitution occurring during the Rh f bathoRh and bathoRh f Rh isomerizations.…”

Section: ' Introductionmentioning

confidence: 99%

The Ultrafast Photoisomerizations of Rhodopsin and Bathorhodopsin Are Modulated by Bond Length Alternation and HOOP Driven Electronic Effects

et al. 2011

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Rhodopsin (Rh) and bathorhodopsin (bathoRh) quantum-mechanics/molecular-mechanics models based on ab initio multiconfigurational wave functions are employed to look at the light induced π-bond breaking and reconstitution occurring during the Rh → bathoRh and bathoRh → Rh isomerizations. More specifically, semiclassical trajectory computations are used to compare the excited (S(1)) and ground (S(0)) state dynamics characterizing the opposite steps of the Rh/bathoRh photochromic cycle during the first 200 fs following photoexcitation. We show that the information contained in these data provide an unprecedented insight into the sub-picosecond π-bond reconstitution process which is at the basis of the reactivity of the protein embedded 11-cis and all-trans retinal chromophores. More specifically, the data point to the phase and amplitude of the skeletal bond length alternation stretching mode as the key factor switching the chromophore to a bonding state. It is also confirmed/found that the phase and amplitude of the hydrogen-out-of-plane mode controls the stereochemical outcome of the forward and reverse photoisomerizations.

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Section: ' Introductionmentioning

confidence: 99%

The Ultrafast Photoisomerizations of Rhodopsin and Bathorhodopsin Are Modulated by Bond Length Alternation and HOOP Driven Electronic Effects

et al. 2011

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“…25) is a well tested and computationally feasible method to study non-adiabatic molecular dynamics (NA-MD) simulations. [26][27][28][29][30][31][32] It enables a separate treatment of electronic (quantum) and nuclear (classical) subsystems. At any given time, the nuclei evolve on a potential energy surface (PES) defined by a single electronic state.…”

Section: Introductionmentioning

confidence: 99%

Shishiodoshi unidirectional energy transfer mechanism in phenylene ethynylene dendrimers

Fernández-Alberti

Roitberg²,

Kleiman³

et al. 2012

The Journal of Chemical Physics

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Non-adiabatic excited-state molecular dynamics is used to study the ultrafast intramolecular energy transfer between two-, three-, and four-ring linear polyphenylene ethynylene chromophore units linked through meta-substitutions. Twenty excited-state electronic energies, with their corresponding gradients and nonadiabatic coupling vectors were included in the simulations. The initial laser excitation creates an exciton delocalized between the different absorbing two-ring linear PPE units. Thereafter, we observe an ultrafast directional change in the spatial localization of the transient electronic transition density. The analysis of the intramolecular flux of the transition density shows a sequential through-bond two-ring→three-ring→four-ring transfer as well as an effective through-space direct two-to-four ring transfer. The vibrational excitations of C≡C stretching motions change according to that. Finally, a mechanism of unidirectional energy transfer is presented based on the variation of the energy gaps between consecutive electronic excited states in response to the intramolecular flux of the transition density. The mechanism resembles a Shishiodoshi Japanese bamboo water fountain where, once the electronic population has been transferred to the state directly below in energy, the two states decouple thereby preventing energy transfer in the opposite direction.

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“…The main difficulty of developing such empirical excited state force fields stems from the relative scarcity of experimental data and the limitations of quantum chemical approaches. For this reason, studies of excited state MD have been rather restricted within direct dynamics for small systems [30][31][32][33], where the use of parameter-based force field is avoided by construction. Recently, however, there have been numerous progresses in developing quantum chemical methodologies for reliably and efficiently describing electronic excited states [34][35][36][37][38][39][40][41][42].…”

mentioning

confidence: 99%

Development of force field parameters for oxyluciferin on its electronic ground and excited states

Song

Rhee

2010

Int J of Quantum Chemistry

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Construction of force field parameters of the oxyluciferin molecule on its electronic ground and excited states is presented. Several new approaches are introduced for more reliable parameterization: argon-scanning, Hessian matching, and constrained-group parameterization. The Ar-scanning approach is for fitting Lennard-Jones parameters so that the constructed force field can mimic the changes in ab initio energy of oxyluciferin-argon pair at various argon positions. The Hessian matching procedure is to closely reproduce the second derivative matrix of the bonded interaction terms of the force field functions, in comparison with the quantum chemically obtained results. The constrained-group algorithm is applied for both of these approaches to enable an automated atom-type-based parameterization. For complete description of the force field of the oxyluciferin molecule, we have also adopted the second order perturbatively corrected one-particle density matrices to obtain the atomic partial charges within the conventional framework of the restrained electrostatic potential fit. With the availability of the full force field parameter sets, the differences in condensed-phase dynamics on the two states can be investigated. As a simple demonstration, molecular dynamics simulations of aqueous oxyluciferin solution have been performed. The surrounding water structures for the two cases are analyzed by inspecting both the static solvent distribution functions as well as time variation of solvent-solute interaction. The contributions of charge-charge and dispersive interactions toward the solvation dynamics are also discussed.

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Azomethane: Nonadiabatic Photodynamical Simulations in Solution

Cited by 52 publications

References 43 publications

The Ultrafast Photoisomerizations of Rhodopsin and Bathorhodopsin Are Modulated by Bond Length Alternation and HOOP Driven Electronic Effects

The Ultrafast Photoisomerizations of Rhodopsin and Bathorhodopsin Are Modulated by Bond Length Alternation and HOOP Driven Electronic Effects

Shishiodoshi unidirectional energy transfer mechanism in phenylene ethynylene dendrimers

Development of force field parameters for oxyluciferin on its electronic ground and excited states

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