Structural dynamics upon photoinduced charge transfer in N,N,N',N'-tetramethylmethylenediamine.

The ultrafast structural motion linked to the charge transfer process in Rydberg excited N,N,N',N'-tetramethylmethylenediamine (TMMDA) has been monitored in real time using femtosecond time-resolved photoelectron imaging coupled with quantum chemical calculations. Optical excitation to the 3 s Rydberg state initially populates the charge on one of the two amine groups, resulting in a charge-localized structure in the Franck-Condon (FC) region. As the wavepacket evolves on the 3 s potential surface, the molecular geometry changes with time, leading to the corresponding variation in the charge distribution. The ensuing structural evolution yields two distinct conformers GG+ and TT+ (see text for nomenclature), both with the charge delocalized between the two nitrogen atoms. By virtue of the sensitivity of the Rydberg electron binding energy (BE) on the nuclear geometry, the time-dependent BE spectrum offers an intuitive mapping of the charge transfer reaction that leads from the initially prepared charge-localized GG-FC structure to the fully charge-delocalized GG+ and TT+ structures. Complementary computations provide evidence that through-space interaction is responsible for the charge delocalization in the GG+ and TT+ structures.

Non-adiabatic dynamics of Rydberg-excited diethylamine.

Femtosecond time-resolved photoelectron spectroscopy was employed to investigate the ultrafast non-adiabatic dynamics of diethylamine (DEA). Following the direct excitations of the two main conformational structures (i.e., TT and TG) of DEA to the 3p Rydberg states at 200 nm, DEA undergoes internal conversion to the 3s state with ∼68 fs, which is similar to previously relaxation pathways of several secondary and tertiary amines. Subsequent dynamics on the 3s Rydberg state evolves along the NH stretching coordinate and is then accompanied by the breaking of the NH bond in about 120 fs, rather than the cleavage of the NC, or CC bonds as well as the conformational transformations between the TT and TG conformers on the 3s states. Theoretically, we reveal the pre-dissociative nσ* character evolving along the NH stretching coordinate within the 3s state as DEA dissociates to yield H atom products. As contrasted to the well-known conformational NC bond rotation motions in systems such as tertiary amines, the non-adiabatic relaxation of the 3s state of DEA is predominantly characterized by the NH bond dissociation process.

Liquid-microjet photoelectron imaging spectrometry for liquid aqueous solutions.

A new liquid-microjet photoelectron imaging (PEI) spectrometer has been constructed that combines the liquid-microjet technique with velocity-map imaging. This novel method enables us to simultaneously measure the energy and angular distributions of the photoelectrons produced from highly volatile liquid solutions. The capability of the spectrometer has been demonstrated by recording the photoelectron image of the aqueous 2-furfural. To our knowledge, this is the first time that the PEI of liquid aqueous solutions has succeeded.

Identification of a bridge-specific intramolecular exciton dissociation pathway in donor-π-acceptor alternating conjugated polymers.

Intramolecular exciton dissociation is critical for high efficient mobile charge carrier generations in organic solar cells. Yet despite much attention, the effects of π bridges on exciton dissociation dynamics in donor-π-acceptor (D-π-A) alternating conjugated polymers remain still unclear. Here, using a combination of femtosecond time-resolved transient absorption (TA) spectroscopy and steady-state spectroscopy, we track ultrafast intramolecular exciton relaxation dynamics in three D-π-A alternating conjugated polymers which were synthesized by Qin's group and named HSD-A, HSD-B, HSD-C. It is found that the addition of thiophene unit as π bridges will lead to the red shift of steady-state absorption spectrum. Importantly, we reveal the existence of a new intramolecular exciton dissociation pathway mediated by a bridge-specific charge transfer (CT') state with the TA fingerprint peak at 1200 nm in π-bridged HSD-B and HSD-C. This CT' state results in higher electron capture rates for HSD-B and HSD-C as compared to HSD-A. Depending on the proportion of CT' state and nongeminate recombination are important step for the understanding of high power conversion efficiencies in HSD-B than in HSD-C. We propose that this bridge-specific exciton dissociation pathway plays an important role in ultrafast intramolecular exciton dissociation of organic photovoltaic material D-π-A alternating conjugated polymers.

Femtosecond time-resolved observation of butterfly vibration in electronically excited o-fluorophenol.

The butterfly vibration during the hydrogen tunneling process in electronically excited o-fluorophenol has been visualized in real time by femtosecond time-resolved ion yield spectroscopy coupled with time-resolved photoelectron imaging technique. A coherent superposition of out-of-plane C-F butterfly motions is prepared in the first excited electronic state (S1). As the C-F bond vibrates with respect to the aromatic ring, the nuclear geometry varies periodically, leading to the corresponding variation in the photoionization channel. By virtue of the more favorable ionization probability from the nonplanar minimum via resonance with the Rydberg states, the evolution of the vibrational wave packet is manifested as a superimposed beat in the parent-ion transient. Moreover, time-resolved photoelectron spectra offer a direct mapping of the oscillating butterfly vibration between the planar geometry and nonplanar minimum. The beats for the photoelectron peaks originating from the planar geometry are out of phase with those from the nonplanar minimum. Our results provide a physically intuitive and complete picture of the oscillatory flow of energy responsible for the coherent vibrational motion on the excited state surface.

Real-time visualization of the vibrational wavepacket dynamics in electronically excited pyrimidine via femtosecond time-resolved photoelectron imaging.

The vibrational wavepacket dynamics at the very early stages of the S1-T1 intersystem crossing in photoexcited pyrimidine is visualized in real time by femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. A coherent superposition of the vibrational states is prepared by the femtosecond pump pulse at 315.3 nm, resulting in a vibrational wavepacket. The composition of the prepared wavepacket is directly identified by a sustained quantum beat superimposed on the parent-ion transient, possessing a frequency in accord with the energy separation between the 6a1 and 6b2 states. The dephasing time of the vibrational wavepacket is determined to be 82 ps. More importantly, the variable Franck-Condon factors between the wavepacket components and the dispersed cation vibrational levels are experimentally illustrated to identify the dark state and follow the energy-flow dynamics on the femtosecond time scale. The time-dependent intensities of the photoelectron peaks originated from the 6a1 vibrational state exhibit a clear quantum beating pattern with similar periodicity but a phase shift of π rad with respect to those from the 6b2 state, offering an unambiguous picture of the restricted intramolecular vibrational energy redistribution dynamics in the 6a1/6b2 Fermi resonance.

Superexcited State Dynamics of OCS: An Experimental Identification of Three Competing Decay Channels among Autoionization, Internal Conversion, and Neutral Predissociation.

The 7sσ and 6pσ superexcited Rydberg states of OCS belonging to series converging onto the B̃2Σ+ ionic limit have been successfully prepared by three-photon UV excitation, and their ensuing competing relaxation processes have been probed by a time-delayed IR ionization pulse. The time profiles of S+ ions, which encode their fragmentation mechanism, are only observable at high pump intensities, thus providing unique experimental identification of the neutral predissociation channel producing S* atoms. Benefiting from this feature and by comparison with the time behavior of OCS+ ions, three competing relaxation channels are identified: autoionization associated with both X̃2Π and Ã2Π ionic states; internal conversion to isoenergetic RA states, the deactivation of which manifests as a picosecond decay in the time profile of OCS+ ions; picosecond neutral predissociation appearing as a nondecaying plateau in the time profiles of S+ ions.

Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene.

Ultrafast electronic relaxation processes following two photoexcitation of 400nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of ~85±10fs and 2.4±0.3ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

Study of ultrafast dynamics of 2-picoline by time-resolved photoelectron imaging.

The dynamics of electronically excited states in 2-picoline is studied using femtosecond time-resolved photoelectron imaging spectroscopy. The internal conversion from the S(2) state to the vibrationally excited S(1) state is observed in real time. The secondarily populated high vibronic S(1) state deactivates further to the S(0) state. Photoelectron energy and angular distributions reveal the feature of ionization from the singlet 3p Rydberg states. In addition, variation of time-dependent anisotropy parameters indicates the rotational coherence of the molecule.

Real-time visualization of the dynamic evolution of CS2 4d and 6s Rydberg wave packet components.

The dynamic evolution of CS2 4d and 6s Rydberg wave packet components has been experimentally visualized via femtosecond time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. The temporal evolution of the four components of the prepared Rydberg wave packet is directly observed as time-dependent changes of the intensities of different parts in the main photoelectron peak. Furthermore, time-resolved photoelectron angular distributions (PADs) clearly reflect the different component characters of 4d and 6s molecular orbitals. The lifetime of Rydberg wave packets is determined to be about 830fs and their decay is attributed to predissociation. Our results suggest the possibility of directly visualizing and determining the amplitudes and relative phases of different electronic and vibrational wave packet components in polyatomic molecules.