Femtosecond Time-resolved Photoelectron Research Articles

Excited state dynamics of molecules studied with femtosecond time-resolved mass spectrometry and photoelectron imaging

Study of quantum states of molecules, especially the evolution of excited states can help to understand their basic features and the interactions among different states. Furthermore, the information about the chemical reaction process and the interactions among several reaction channels can be obtained. Femtosecond time-resolved mass spectrometry (TRMS) and time-resolved photoelectron imaging (TRPEI), which combine pump-probe technique with time of flight mass spectrometry and photoelectron imaging, are powerful tools for detecting the molecular quantum state and for studying the molecular quantum state interaction and molecular ultrafast dynamics. With these methods, the photochemistry and photophysics mechanism of isolated molecule reaction process can be investigated on a femtosecond time scale. The principles of TRMS and TRPEI are introduced here in detail. On the basis of substantial research achievements in our group, the applications of TRMS and TRPEI are presented in the study of ultrafast internal conversion and intersystem crossing, wavepacket evolution dynamics at excited states of polyatomic molecules, energy transfer process of polyatomic molecules, ultrafast photodissociation dynamics and structural evolution dynamics of molecular excited states. In the study of ultrafast internal conversion and intersystem crossing, the methyl substituted benzene derivatives and benzene halides are discussed as typical molecular systems. In the study of wavepacket evolution dynamics at excited states of polyatomic molecules, the real-time visualization of the dynamic evolution of CS2 4d and 6s Rydberg wave packet components, the vibrational wave packet dynamics in electronically excited pyrimidine, the rotational wave packet revivals and field-free alignment in excited o-dichlorobenzene are reported. In order to discuss the energy transfer process of polyatomic molecules, the intramolecular vibrational energy redisctribution between different vibrational states in p-difluorobenzene in the S1 low-energy regime and the intramolecular energy transfer between different electronic states in excited cyclopentanone are presented. For the study of ultrafast photodissociation dynamics, the dissociation constants and dynamics of the A band and even higher Rydberg states are investigated for the iodine alkanes and iodine cycloalkanes. Structural evolution dynamics of molecular excited states is the main focus of our recent research. The structural evolution dynamics can be extracted from the coherent superposition preparation of quantum states and the observation of quantum beat phenomenon, by taking 2, 4-difluorophenol and o-fluorophenol as examples. Time-dependent photoelectron peaks originating from the planar and nonplanar geometries in the first excited state in 2, 4-difluorophenol exhibit the clear beats with similar periodicities but a phase shift of π rad, offering an unambiguous picture of the oscillating nuclear motion between the planar geometry and the nonplanar minimum. Also, the structural evolution dynamics in o-fluorophenol via the butterfly vibration between planar geometry and nonplanar minimum is mapped directly. Finally, the potential developments and further possible research work and future directions of these techniques and researches are prospected.

Tracking the relaxation of 2,5-dimethylpyrrole by femtosecond time-resolved photoelectron and photoion detection.

The relaxation of 2,5-dimethylpyrrole after excitation in the 290-239 nm range, which covers the weak absorption of the S1 (1)A2 πσ* state, dissociative along the N-H bond, and the stronger band mostly attributed to the (1)B2 ππ* state, has been investigated by time-resolved ion and photoelectron techniques. The measurements yield an invariant lifetime of ∼55 fs for the (1)πσ* state, after preparation in its Franck-Condon region with increasing vibrational content. This ultrafast rate indicates that, contrary to the observations made in pyrrole (Roberts et al. Faraday Discuss. 2013, 163, 95-116), the molecule reaches the dissociative part of the potential without any barrier effect, although calculations predict the latter to be higher than in the pyrrole case. The results are rationalized in terms of a barrier free multidimensional pathway that very likely involves out-of-plane vibrations. Additionally, a lifetime of ∼100 fs is found after excitation along the higher (1)B2 ππ* ← S0 transition. The relaxation of this state by coupling to a very short living S1 (1)πσ* state, or by alternative routes, is discussed in the light of the collected photoelectron measurements.

A mobile UHV-system designed for femtosecond time, energy and spin resolved photoelectron spectroscopy

We report on the design and tests of a completely mobile photoemission end station for femtosecond time, energy and spin resolved magnetodynamics experiments. The setup is designed for the use at free-electron laser (FEL) x-ray beamlines as well as at synchrotron facilities. In situ sample preparation in an adjacent UHV chamber is performed. The assembly can be altered to obtain energy resolved measurements with the help of a hemispherical electron energy analyzer or to obtain energy integrated measurements by inserting an electron transfer lens system. The magnetic information is obtained by spin analysis with a 50 kV Mott detector. The setup is tested in house with an electron gun, at the Swiss Light Source (SLS) and has been used at the FEL at FLASH in Hamburg. Results show the practicability of the system and exemplarily the kinetic energy dependent polarization of the low energy secondary electrons emitted from a 15 ML iron film on W(110) is presented.

Inelastic Coulomb Scatterings of Doped Armchair Carbon Nanotubes

For doped armchair carbon nanotubes, the free electrons in the conduction bands would cause the intraband single-particle and collective excitations. Both kinds of excitations would be split into two modes because of two different Fermi-momentum states (kF'S). The excited carriers might be deexcited through such Coulomb excitations. Regarding the case where the transferred momentum L = 0, the two single-particle and the lower-frequency collective excitation modes could be the efficient deexcitation channels. In the lowest bands, the decay rates of the electron states exhibit weak Fermi energy (E(F)) dependence, but the decay rates of the hole states become greater with the increase of E(F) except for the right-side k(F). Concerning the states in the higher bands, the L not equal 0 excitations also take part in the deexcitation processes. Both the electron and hole states have the same decay rates except for the case where the carriers decay to the lowest states. The decay rates contrast sharply with those of undoped carbon nanotubes and two-dimensional intercalated graphenes. It is domenated by the Fermi energy, the geometric structure and the dimensionalities. The femtosecond time-resolved photoelectron, transmission and fluorescence spectroscopies could be used to verify the predicted results.

Non-adiabatic intramolecular and photodissociation dynamics studied by femtosecond time-resolved photoelectron and coincidence imaging spectroscopy

Time-resolved photoelectron spectroscopy (TRPES) is emerging as a useful tool for the study of non-adiabatic dynamics in isolated polyatomic molecules and clusters due to its sensitivity to both electronic and vibrational dynamics. A powerful extension of TRPES, coincidence imaging spectroscopy (CIS), based upon femtosecond time-resolved 3D momentum vector imaging of both photoions and photoelectrons in coincidence, is a new technique for the study of complex dissociative processes. Here we show how these spectroscopies can be used to study both non-adiabatic intramolecular and photodissociation dynamics in polyatomic molecules. Intramolecular dynamics in the alpha, beta-enones acrolein, crotonaldehyde and methyl vinyl ketone are studied using both TRPES and laser-induced fluorescence of HCO(X) product yields. The location of the methyl group is seen to have very dramatic effects on the relative electronic relaxation rates and the HCO(X) yield. Applying both TRPES and CIS to the 200 nm and 209 nm photodissociation of the nitric oxide dimer, (NO)2, we observe the fs time-scale evolution of the excited parent neutral via its photoelectron spectrum and the emergence of the NO(A) photofragment including its energy and angular distributions.