Viscosity dependence and solvent effects in the photoisomerization of <i>cis</i>-stilbene: Insight from a molecular dynamics study with an <i>ab initio</i> potential-energy function

Berweger, Christian D.; Gunsteren, Wilfred F. van; Müller‐Plathe, Florian

doi:10.1063/1.480242

Cited by 14 publications

(10 citation statements)

References 42 publications

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“…9 The most intriguing result, besides the one that the rate of isomerization is independent of solvent in the first 40 ps, in contrast to experiment, 10 is that the excited trans and gauche minimum (the latter is obtained in the course of geometry optimization starting from the cis side) are separated by a barrier which corresponds to the so-called perpendicular stilbene. In other words, the S 1 minimum at 90°, if it exists at all, should originate from another singlet state.…”

Section: Resultsmentioning

confidence: 72%

Resonance Raman spectra of deuterated cis‐stilbene

Baranović

2001

J Raman Spectroscopy

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Resonance Raman intensities of perdeuterated cis-stilbene were measured using excitation at 266 nm. For the six analysed bands at 1612, 1564, 1537, 1372, 1325 and 958 cm −1 , no large changes in intensity distribution relative to the parent compound were found in accordance with the scrambling coefficients showing that the corresponding modes n 7 , n 8 , n 9 , n 10 , n 11 and n 15 of d 12 -cis-stilbene have all of the Raman activity. The S 1 equilibrium geometry and vibrational force field for cis-stilbene were calculated at the CIS/6-31G(d) level and the vibrational assignment for the parent compound and some of its symmetrically substituted isotopomers is considered. The obtained excited-state geometry distortions are large, preventing the use of a simple displacement equation for relative Raman intensities. Therefore, in their determination the gradients of the S 1 state, potential energy surfaces calculated at the ground-state geometry were also used. Even in its simplest form this approach reproduces the experiment fairly reasonably.

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Section: Resultsmentioning

confidence: 72%

Resonance Raman spectra of deuterated cis‐stilbene

Baranović

2001

J Raman Spectroscopy

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“…Various models and approximate approaches have, of course, already been employed in dynamical simulations of the photoisomerization of cis-stilbene [7,21,[24][25][26][27][28]. Examples include the quasiclassical molecular dynamics approach of Frederick and coworkers [24][25][26] and the ab initio potential energy surface approach of van Gunsteren and coworkers [7,27,28].…”

Section: Introductionmentioning

confidence: 99%

Detailed dynamics of a complex photochemical reaction: Cis–trans photoisomerization of stilbene

Dou

Allen

2003

The Journal of Chemical Physics

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Detailed simulations are reported for the dynamics of electrons and nuclei during the cis to trans photoisomerization of stilbene. Our method, which employs a semiclassical description of both the nuclear motion and the radiation field, is described in the text. After excitation of electrons from the HOMO to the LUMO by a femtosecond-scale laser pulse, two principal avoided crossings are observed between the HOMO and LUMO levels, each of which leads to substantial depopulation of the LUMO. Based on our results and those of other groups, we propose that the first such HOMO-LUMO coupling can lead to the formation of 4a,4b-dihydrophenanthrene (DHP). The second coupling, on the other hand, leads to the formation of trans-stilbene. It is found that pyramidalization of the two carbon atoms of the vinyl group is involved significantly in both couplings, and that rotation of the two phenyl rings, together with their interaction, plays an important role in the first coupling. The occurrence along the same trajectory of two couplings, one leading to DHP and the other leading to isomerization, is a significant observation, and one which indicates that further theoretical and experimental investigations would be of considerable interest.

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“…Although the present study does not identify any other true minimum for the cis isomer, the experimental study on cis-stilbene in argon clusters 39 has observed an S 1 local minimum in the cis region. Furthermore, the semiempirical 37 and configuration interaction singles (CIS) 58,59 methods have identified a cis minimum. It is not surprising that dynamic correlation stabilizes the DHP minimum with respect to the cis minimum and/or lowers the barrier of DHP formation on the S 1 PES.…”

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confidence: 99%

Photoisomerization of Stilbene: A Spin-Flip Density Functional Theory Approach

2011

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The photoisomerization process of 1,2-diphenylethylene (stilbene) is investigated using the spin-flip density functional theory (SFDFT), which has recently been shown to be a promising approach for locating conical intersection (CI) points (Minezawa, N.; Gordon, M. S. J. Phys. Chem. A2009, 113, 12749). The SFDFT method gives valuable insight into twisted stilbene to which the linear response time-dependent DFT approach cannot be applied. In contrast to the previous SFDFT study of ethylene, a distinct twisted minimum is found for stilbene. The optimized structure has a sizable pyramidalization angle and strong ionic character, indicating that a purely twisted geometry is not a true minimum. In addition, the SFDFT approach can successfully locate two CI points: the twisted-pyramidalized CI that is similar to the ethylene counterpart and another CI that possibly lies on the cyclization pathway of cis-stilbene. The mechanisms of the cis-trans isomerization reaction are discussed on the basis of the two-dimensional potential energy surface along the twisting and pyramidalization angles. Disciplines Chemistry CommentsReprinted (adapted) with permission from

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Viscosity dependence and solvent effects in the photoisomerization of cis-stilbene: Insight from a molecular dynamics study with an ab initio potential-energy function

Cited by 14 publications

References 42 publications

Resonance Raman spectra of deuterated cis‐stilbene

Resonance Raman spectra of deuterated cis‐stilbene

Detailed dynamics of a complex photochemical reaction: Cis–trans photoisomerization of stilbene

Photoisomerization of Stilbene: A Spin-Flip Density Functional Theory Approach

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