Electronic Spectroscopy and Ultrafast Energy Relaxation Pathways in the Lowest Rydberg States of Trimethylamine

Cardoza, Job D.; Rudakov, Fedor; Weber, Peter M.

doi:10.1021/jp8041236

Cited by 49 publications

(52 citation statements)

References 40 publications

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“…Importantly, the 3s feature of PENNA shows a unique time-dependent shape, which we investigate further below. In contrast, the 3s peak of CENNA remains steady, much as we have observed in other amines that lack further dynamics in 3s (e.g., trimethyl amine, 31 …”

Section: Resultssupporting

confidence: 67%

Dissociative Energy Flow, Vibrational Energy Redistribution, and Conformeric Structural Dynamics in Bifunctional Amine Model Systems

2010

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Time-resolved multiphoton ionization mass spectrometry coupled with Rydberg Fingerprint Spectroscopy (RFS) has been used to analyze the structural and electronic dynamics of N,N-dimethylphenethylamine (PENNA) and N,N-dimethylcyclohexethylamine (CENNA). In PENNA, the molecule converts from 3p to 3s on a time scale of 149 fs, a process that is reflected in the mass spectrum as the onset of fragmentation. Once in 3s, the overall signal intensity of the PENNA 3s signal shows biexponential decay kinetics, which is attributed to the electronic curve crossing from the Rydberg state to a dissociative antibonding orbital of the ethylenic bridge. This curve crossing exemplifies a possible fragmentation pathway observed in electron capture dissociation of proteins. The initially fast reaction (1.3 ps) is greatly slowed down as a result of an apparent relaxation process with a 5.6 ps time constant. The electron binding energy of the 3s Rydberg state of PENNA is observed to shift with a time constant of 4.8 ps, which is correlated to a cation-π interaction driven conformeric rearrangement.

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Section: Resultssupporting

confidence: 67%

Dissociative Energy Flow, Vibrational Energy Redistribution, and Conformeric Structural Dynamics in Bifunctional Amine Model Systems

2010

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“…The experimental design used in this study has been described previously [26][27][28][29][30]. Briefly, CHD was cooled to 0 • C, seeded into a stream of helium carrier gas, and expanded through a 100 μm nozzle orifice and a 150 μm skimmer.…”

Section: Experimental Methodsmentioning

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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“…Ultrafast measurements typically involve a pump-probe scheme, where a laser pump pulse prepares an initial wavefunction, whose subsequent time evolution is probed at a sequence of delay-times [15][16][17][18][19][20][21][22][23][24]. Depending on the experimental situation, the wavepacket may be of electronic [25,26], nuclear [27], or mixed nuclear-electronic [28] nature.…”

Section: Introductionmentioning

confidence: 99%

Fundamental Limits on Spatial Resolution in Ultrafast X-ray Diffraction

Kirrander

Weber

2017

Applied Sciences

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X-ray Free-Electron Lasers have made it possible to record time-sequences of diffraction images to determine changes in molecular geometry during ultrafast photochemical processes. Using state-of-the-art simulations in three molecules (deuterium, ethylene, and 1,3-cyclohexadiene), we demonstrate that the nature of the nuclear wavepacket initially prepared by the pump laser, and its subsequent dispersion as it propagates along the reaction path, limits the spatial resolution attainable in a structural dynamics experiment. The delocalization of the wavepacket leads to a pronounced damping of the diffraction signal at large values of the momentum transfer vector q, an observation supported by a simple analytical model. This suggests that high-q measurements, beyond 10-15 Å −1 , provide scant experimental payback, and that it may be advantageous to prioritize the signal-to-noise ratio and the time-resolution of the experiment as determined by parameters such as the repetition-rate, the photon flux, and the pulse durations. We expect these considerations to influence future experimental designs, including source development and detection schemes.

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Electronic Spectroscopy and Ultrafast Energy Relaxation Pathways in the Lowest Rydberg States of Trimethylamine

Cited by 49 publications

References 40 publications

Dissociative Energy Flow, Vibrational Energy Redistribution, and Conformeric Structural Dynamics in Bifunctional Amine Model Systems

Dissociative Energy Flow, Vibrational Energy Redistribution, and Conformeric Structural Dynamics in Bifunctional Amine Model Systems

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

Fundamental Limits on Spatial Resolution in Ultrafast X-ray Diffraction

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