Time-resolved photoionization spectroscopy of mixed Rydberg-valence states: indole case study

2015 ◽  
Vol 17 (40) ◽  
pp. 26659-26669 ◽  
Author(s):  
Magdalena M. Zawadzki ◽  
James O. F. Thompson ◽  
Emma A. Burgess ◽  
Martin J. Paterson ◽  
Dave Townsend
Keyword(s):  
Gas Phase ◽  
Relaxation Dynamics ◽  
Photoelectron Imaging ◽  
Time Resolved ◽  
Mechanistic Insight ◽  
Valence States ◽  
Insight Into

Time-resolved photoelectron imaging reveals subtle new mechanistic insight into the ultraviolet relaxation dynamics of gas-phase indole.

Observation of multi-channel non-adiabatic dynamics in aniline derivatives using time-resolved photoelectron imaging

2016 ◽  
Vol 194 ◽  
pp. 185-208 ◽  
Author(s):  
Magdalena M. Zawadzki ◽  
Marco Candelaresi ◽  
Lisa Saalbach ◽  
Stuart W. Crane ◽  
Martin J. Paterson ◽  
...  
Keyword(s):  
Excited State ◽  
Angular Distributions ◽  
Relaxation Dynamics ◽  
Photoelectron Imaging ◽  
Time Resolved ◽  
Valence States ◽  
Ultimate Fate ◽  
Site Selective ◽  
Photoelectron Angular Distributions ◽  
Electronic Character

We present results from a recent time-resolved photoelectron imaging (TRPEI) study investigating the non-adiabatic relaxation dynamics of N,N-dimethylaniline (N,N-DMA) and 3,5-dimethylaniline (3,5-DMA) following excitation at 240 nm. Analysis of the experimental data is supported by ab initio coupled-cluster calculations evaluating excited state energies and the evolution of several excited state physical properties as a function of N–H/N–CH3 bond extension – a critical reaction coordinate. The use of site-selective methylation brings considerable new insight to the existing body of literature concerning photochemical dynamics in the related system aniline at similar excitation wavelengths. The present work also builds on our own previous investigations in the same species at 250 nm. The TRPEI method provides highly differential energy- and angle-resolved data and, in particular, the temporal evolution of the photoelectron angular distributions afforded by the imaging approach offers much of the new dynamical information. In particular, we see no clear evidence of the second excited 2ππ* state non-adiabatically coupling to the lower-lying S1(ππ*) state or the mixed Rydberg/valence S2(3s/πσ*) state. This, in turn, potentially raises some unresolved questions about the overall nature of the dynamics operating in these systems, especially in regard to the 2ππ* state's ultimate fate. More generally, the findings for the aromatic systems N,N-DMA and 3,5-DMA, taken along with our recent TRPEI results for several aliphatic amine species, highlight interesting questions about the nature of electronic character evolution in mixed Rydberg-valence states as a function of certain key bond extensions and the extent of system conjugation. We begin exploring these ideas computationally for a systematically varied series of tertiary amines.

scholarly journals Using time-resolved photoelectron spectroscopy to unravel the electronic relaxation dynamics of photoexcited molecules

2018 ◽  
Vol 47 (2) ◽  
pp. 309-321 ◽  
Author(s):  
Helen H. Fielding ◽  
Graham A. Worth
Keyword(s):  
Quantum Chemistry ◽  
Gas Phase ◽  
Photoelectron Spectroscopy ◽  
Electronic Relaxation ◽  
Relaxation Dynamics ◽  
Time Resolved ◽  
Insight Into

Time-resolved photoelectron spectroscopy measurements combined with quantum chemistry and dynamics calculations allow unprecedented insight into the electronic relaxation mechanisms of photoexcited molecules in the gas-phase.

Unraveling the electronic relaxation dynamics in photoexcited 2,4-difluoroaniline via femtosecond time-resolved photoelectron imaging

2018 ◽  
Vol 148 (14) ◽  
pp. 144311 ◽  
Author(s):  
Fengzi Ling ◽  
Shuai Li ◽  
Jie Wei ◽  
Kai Liu ◽  
Yanmei Wang ◽  
...  
Keyword(s):  
Electronic Relaxation ◽  
Relaxation Dynamics ◽  
Photoelectron Imaging ◽  
Time Resolved

Key Mechanistic Insight into the Direct Gas-Phase Epoxidation of Propylene by the RuO2-CuO-NaCl/SiO2Catalyst

ChemCatChem ◽  
2014 ◽  
pp. n/a-n/a ◽  
Author(s):  
Anusorn Seubsai ◽  
Bahman Zohour ◽  
Daniel Noon ◽  
Selim Senkan
Keyword(s):  
Gas Phase ◽  
Epoxidation Of Propylene ◽  
Mechanistic Insight ◽  
Insight Into

C6− electronic relaxation dynamics probed via time-resolved photoelectron imaging

2004 ◽  
Vol 121 (8) ◽  
pp. 3515-3526 ◽  
Author(s):  
Arthur E. Bragg ◽  
Jan R. R. Verlet ◽  
Aster Kammrath ◽  
Daniel M. Neumark
Keyword(s):  
Electronic Relaxation ◽  
Relaxation Dynamics ◽  
Photoelectron Imaging ◽  
Time Resolved

scholarly journals Ultrafast Relaxation Dynamics of the S1 (nπ*) State and the 3p and 3d Rydberg States in Cyclohexanone by Femtosecond Photoelectron Imaging

2019 ◽  
Author(s):  
Ole Hüter ◽  
Niklas Helle ◽  
Friedrich Temps
Keyword(s):  
Imaging Spectroscopy ◽  
Rydberg States ◽  
Population Transfer ◽  
Relaxation Dynamics ◽  
Photoelectron Imaging ◽  
Time Resolved ◽  
Flight Mass Spectrometry ◽  
Vibronic Interactions ◽  
Photon Excitation ◽  
Photoelectron Imaging Spectroscopy

<div>The radiationless decay dynamics of the S1 (nπ*) state and the 3p and 3d Rydberg states of cyclohexanone are investigated using femtosecond time-resolved time-of- flight mass spectrometry and photoelectron imaging spectroscopy. After two-photon excitation of the 3p and 3d states, an ultrafast population transfer to the 3s state is observed within < 120 fs. We ascribe this behavior to strong vibronic interactions of the excited Rydberg states with the <sup>1</sup>ππ* valence state that enable an ultrafast population transfer via an avoided crossing and the subsequent passage of a conical intersection between the respective electronic states. Eventually, the 3s state deactivates by internal conversion to the S<sub>1</sub> (nπ*) state, which in turn is found to be long-lived with a decay time of ~ 300 - 800 ps.</div>

scholarly journals Time-resolved photoelectron imaging of the isolated deprotonated nucleotides

2014 ◽  
Vol 5 (10) ◽  
pp. 3963-3975 ◽  
Author(s):  
Adam S. Chatterley ◽  
Christopher W. West ◽  
Vasilios G. Stavros ◽  
Jan R. R. Verlet
Keyword(s):  
Photoelectron Spectroscopy ◽  
Relaxation Dynamics ◽  
Photoelectron Imaging ◽  
Time Resolved

Time-resolved photoelectron spectroscopy of deprotonated nucleotides provides new insights into their relaxation dynamics.

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