Ground state recovery and molecular structure upon ultrafast transition through conical intersections in cyclic dienes

Rudakov, Fedor; Weber, Peter M.

doi:10.1016/j.cplett.2009.01.058

Cited by 34 publications

(43 citation statements)

References 26 publications

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“…If CHD underwent ring opening upon excitation at 207 nm, this fraction of CHD would be unavailable for excitation via the same Rydberg level and therefore cause a depletion in the CHD spectrum. Such a depletion has previously been observed in a (3 + 2) investigation [25]. Figure 4 shows the two-color spectra with time delays before and after the ring opening, as well as a difference spectrum in the (4 + 2) experiment.…”

Section: Resultsmentioning

confidence: 84%

Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

Buhler

Minitti

Deb

et al. 2011

Journal of Atomic, Molecular, and Optical Physics

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The ultrafast dynamics of 1,3-cyclohexadiene has been investigated via structurally sensitive Rydberg electron binding energies and shown to differ upon excitation to the 1B state and the 3p Rydberg state. Excitation of the molecule with 4.63 eV photons into the ultrashort-lived 1B state yields the well-known ring opening to 1,3,5-hexatriene, while a 5.99 eV photon lifts the molecule directly into the 3p-Rydberg state. Excitation to 3p does not induce ring opening. In both experiments, time-dependent shifts of the Rydberg electron binding energy reflect the structural dynamics of the molecular core. Structural distortions associated with 3p-excitation cause a dynamical shift in the p x -and p y -binding energies by 10 and 26 meV/ps, respectively, whereas after excitation into 1B, more severe structural transformations along the ring-opening coordinate produce shifts at a rate of 40 to 60 meV/ps. The experiment validates photoionization-photoelectron spectroscopy via Rydberg states as a powerful technique to observe structural dynamics of polyatomic molecules.

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Section: Resultsmentioning

confidence: 84%

Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

Buhler

Minitti

Deb

et al. 2011

Journal of Atomic, Molecular, and Optical Physics

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“…This is especially important because a profound understanding of photoinduced dynamics almost always necessitates a detailed comparison of experiment with theory. Many model systems have been investigated by time-resolved experiments [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] or dynamical simulations. [20][21][22][23][24][25][26] We believe that fundamental questions could be answered more easily by joint studies connecting experimental approaches with such simulations.…”

Section: Introductionmentioning

confidence: 99%

Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

Wolf

Kuhlman

Schalk

et al. 2014

Phys. Chem. Chem. Phys.

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“…1 In particular molecules possessing conjugated carbon-carbon double bonds participate in a plethora of reactions induced by light such as photoisomerisation, 2-11 electrocyclic ring-opening and closing, [12][13][14][15][16][17][18][19][20] sigmatropic rearrangement [21][22][23] and cycloaddition. 12,24 Polyenes are prominent examples of such systems e.g.…”

Section: Introductionmentioning

confidence: 99%

Between ethylene and polyenes - the non-adiabatic dynamics of cis-dienes

et al. 2012

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Perturbation theory (MS-MR-CASPT2) treatment of the electronic structure, we have simulated the non-adiabatic excited state dynamics of cyclopentadiene (CPD) and 1,2,3,4-tetramethyl-cyclopentadiene (Me 4 -CPD) following excitation to S 1 . It is observed that torsion around the carbon-carbon double bonds is essential in reaching a conical intersection seam connecting S 1 and S 0 . We identify two timescales; the induction time from excitation to the onset of population transfer back to S 0 (CPD: $25 fs, Me 4 -CPD: $71 fs) and the half-life of the subsequent population transfer (CPD: $28 fs, Me 4 -CPD: $48 fs). The longer timescales for Me 4 -CPD are a kinematic consequence of the inertia of the substituents impeding the essential out-of-plane motion that leads to the conical intersection seam. A bifurcation is observed on S 1 leading to population transfer being attributable, in a 5 : 2 ratio for CPD and 7 : 2 ratio for Me 4 -CPD, to two closely related conical intersections. Calculated time-resolved photoelectron spectra are in excellent agreement with experimental spectra validating the simulation results.

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Ground state recovery and molecular structure upon ultrafast transition through conical intersections in cyclic dienes

Cited by 34 publications

References 26 publications

Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

Ultrafast Dynamics of 1,3-Cyclohexadiene in Highly Excited States

Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

Between ethylene and polyenes - the non-adiabatic dynamics of cis-dienes

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