2014
DOI: 10.1039/c4sc01646g
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Ultrafast structural dynamics in Rydberg excited N,N,N′,N′-tetramethylethylenediamine: conformation dependent electron lone pair interaction and charge delocalization

Abstract: Time-resolved Rydberg fingerprint spectroscopy and quantum calculations reveal the structure dependent electron lone pair interaction and charge delocalization in real time.

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Cited by 34 publications
(43 citation statements)
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“…The time-resolved photoelectron spectrum of panel D, which is taken with the highest intensity probe pulses, shows the Rydberg peaks most clearly. Using laser pulses of somewhat longer duration, and concomitantly smaller bandwidth, these 36 and n=3, δ=0.55) did not seem to fit with those of other peaks. In a later investigation of the pump-probe photoelectron spectrum where the pump photon matched the excitation energy of 3p from the ground state (6 eV), the 2.26 eV peak was identified as 3p.…”
Section: Resultsmentioning
confidence: 44%
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“…The time-resolved photoelectron spectrum of panel D, which is taken with the highest intensity probe pulses, shows the Rydberg peaks most clearly. Using laser pulses of somewhat longer duration, and concomitantly smaller bandwidth, these 36 and n=3, δ=0.55) did not seem to fit with those of other peaks. In a later investigation of the pump-probe photoelectron spectrum where the pump photon matched the excitation energy of 3p from the ground state (6 eV), the 2.26 eV peak was identified as 3p.…”
Section: Resultsmentioning
confidence: 44%
“…In principle, it should also be possible to invert the Rydberg level binding energies that we measure here to derive a time-dependent molecular structure. 35,36 However, the computation of binding energies of Rydberg levels converging to the possibly core-excited and highly distorted HT ion, as would be necessary to deduce the structures from the photoelectron experiments, remains challenging for the CHD system. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Experiment A molecular beam was created by flowing helium at 1.5 bar through liquid 1,3-cyclohexadiene (Aldrich, 97%) and expanding the vapor through a 100 µm nozzle orifice and a skimmer.…”
Section: Introductionmentioning
confidence: 99%
“…1 More generally, we note that DABCO (and other TAAs containing two amino groups) have been shown to exhibit additional interactions between the N atom lone pairs (with associated charge delocalization effects). 15,33,34 This adds additional complexity to the dynamics and so a more detailed direct comparison between DABCO and ABCO is not considered further here. The second, much longer-lived fit component t 2 seen at B2.9 eV arises from 3s ionization once this state is populated via internal conversion.…”
Section: Resultsmentioning
confidence: 99%
“…It turns out that quite good estimates of bond energy, as well as band gaps of solids are obtained if the PZ-SIC terms are scaled by a factor of 1/2 during the self-consistent calculations when the PBE functional is used [10,5]. However, this is not satisfactory in many respects; for example, the correct −1/r dependence of the effective potential is not obtained if such scaling is applied, and thus the method is not applicable to, e.g., studies of Rydberg excited states of molecules and clusters of molecules, an application for which PZ-SIC has turned out to be highly successful [12,13,14].…”
Section: Introductionmentioning
confidence: 98%