Centering of ultrafast time-resolved pump–probe electron diffraction patterns

Cardoza, Job D.; Dudek, Raymond C.; Mawhorter, Richard; Weber, Peter M.

doi:10.1016/j.chemphys.2003.12.018

Cited by 25 publications

(17 citation statements)

References 10 publications

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“…Experimental investigations using resonance Raman spectroscopy, 4-9 transient absorption, 8,10-12 laser photoionization, [13][14][15] and pumpprobe electron diffraction [16][17][18][19][20] have been paired with quantum chemical calculations [21][22][23][24][25][26][27] to refine the orbital symmetry concepts developed by Woodward and Hoffman and van der Lugt and Osterhoff. Experimental investigations using resonance Raman spectroscopy, 4-9 transient absorption, 8,10-12 laser photoionization, [13][14][15] and pumpprobe electron diffraction [16][17][18][19][20] have been paired with quantum chemical calculations [21][22][23][24][25][26][27] to refine the orbital symmetry concepts developed by Woodward and Hoffman and van der Lugt and Osterhoff.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopy and femtosecond dynamics of the ring opening reaction of 1,3-cyclohexadiene

Kuthirummal

Rudakov

Evans

et al. 2006

The Journal of Chemical Physics

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The early stages of the ring opening reaction of 1,3-cyclohexadiene to form its isomer 1,3,5-hexatriene, upon excitation to the ultrashort-lived 1 1B2 state, were explored. A series of one-color two-photon ionization/photoelectron spectra reveal a prominent vibrational progression with a frequency of 1350 cm(-1), which is interpreted in a dynamical picture as resulting from the ultrafast wave packet dynamics associated with the ring opening reaction. Photoionization in two-color three-photon and one-color four-photon ionization schemes show an ionization pathway via the same ultrashort-lived 1 1B2 state, and in addition, a series of Rydberg states with quantum defects of 0.93, 0.76, and 0.15, respectively. Using those Rydberg states as probes for the reaction dynamics in a time-resolved pump-probe experiment provides a direct observation of the elusive 2 1A1 state that has been implicated as an intermediate step between the initially excited 1 1B2 state and the ground electronic state. The rise and decay times for the 2 1A1 state were found to be 55 and 84 fs, respectively.

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Section: Introductionmentioning

confidence: 99%

Spectroscopy and femtosecond dynamics of the ring opening reaction of 1,3-cyclohexadiene

Kuthirummal

Rudakov

Evans

et al. 2006

The Journal of Chemical Physics

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“…46,47 Finally, and perhaps most importantly, CHD has been used extensively to demonstrate new techniques and concepts. This includes coherent control, both experiment 43,48,49 and theory, 7,50,51 and a range of new ultrafast imaging techniques 52 such as electron diffraction, [53][54][55][56] X-ray scattering, 44,45 Coulomb explosion, 57 and near-edge X-ray absorption fine structure (NEXAFS). 58 The variety of complementary observations generated by these techniques holds great promise for tying down a complete understanding of this important and complex reaction, for instance by combining X-ray scattering and photoelectron data such as in ref.…”

Section: Introductionmentioning

confidence: 99%

Effects of probe energy and competing pathways on time-resolved photoelectron spectroscopy: the ring-opening of 1,3-cyclohexadiene

Tudorovskaya

Minns

Kirrander

2018

Phys. Chem. Chem. Phys.

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The ring-opening dynamics of 1,3-cyclohexadiene (CHD) following UV excitation is studied using a model based on quantum molecular dynamics simulations with the ab initio multiconfigurational Ehrenfest (AI-MCE) method coupled to the Dyson orbital approach for photoionisation cross sections.Time-dependent photoelectron spectra are calculated for probe photon energies in the range 2-15 eV. The calculations demonstrate the value of universal high-energy probes, capable of tracking the dynamics in full, but also the utility of more selective lower-energy probes with a more restricted ionisation range. The predicted signal, especially with the universal probes, becomes highly convoluted due to the contributions from multiple reaction paths, rendering interpretation challenging unless complementary measurements and theoretical comparisons are available.

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“…While historically static structure determination methods, such as electron diffraction, have been adapted to fast time scales, there are some limitations, for example, relating to the size of the molecular system [10][11][12][13][14]. Rydberg fingerprint spectroscopy (RFS) takes advantage of the fact that the binding energies of electrons in Rydberg states are sensitive towards the arrangement of atoms in the ion core [15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

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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Centering of ultrafast time-resolved pump–probe electron diffraction patterns

Cited by 25 publications

References 10 publications

Spectroscopy and femtosecond dynamics of the ring opening reaction of 1,3-cyclohexadiene

Spectroscopy and femtosecond dynamics of the ring opening reaction of 1,3-cyclohexadiene

Effects of probe energy and competing pathways on time-resolved photoelectron spectroscopy: the ring-opening of 1,3-cyclohexadiene

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

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