Fedor Rudakov

Ultrafast time-resolved electron diffraction with megavolt electron beams

A rf photocathode electron gun is used as an electron source for ultrafast time-resolved pump-probe electron diffraction. The authors observed single-shot diffraction patterns from a 160nm Al foil using the 5.4MeV electron beam from the Gun Test Facility at the Stanford Linear Accelerator. Excellent agreement with simulations suggests that single-shot diffraction experiments with a time resolution approaching 100fs are possible.

Spectroscopy and femtosecond dynamics of the ring opening reaction of 1,3-cyclohexadiene.

The early stages of the ring opening reaction of 1,3-cyclohexadiene to form its isomer 1,3,5-hexatriene, upon excitation to the ultrashort-lived 1 1B2 state, were explored. A series of one-color two-photon ionization/photoelectron spectra reveal a prominent vibrational progression with a frequency of 1350 cm(-1), which is interpreted in a dynamical picture as resulting from the ultrafast wave packet dynamics associated with the ring opening reaction. Photoionization in two-color three-photon and one-color four-photon ionization schemes show an ionization pathway via the same ultrashort-lived 1 1B2 state, and in addition, a series of Rydberg states with quantum defects of 0.93, 0.76, and 0.15, respectively. Using those Rydberg states as probes for the reaction dynamics in a time-resolved pump-probe experiment provides a direct observation of the elusive 2 1A1 state that has been implicated as an intermediate step between the initially excited 1 1B2 state and the ground electronic state. The rise and decay times for the 2 1A1 state were found to be 55 and 84 fs, respectively.

Electronic spectroscopy and ultrafast energy relaxation pathways in the lowest Rydberg States of trimethylamine.

Resonance-enhanced multiphoton ionization photoelectron spectroscopy has been applied to study the electronic spectroscopy and relaxation pathways among the 3p and 3s Rydberg states of trimethylamine. The experiments used femtosecond and picosecond duration laser pulses at wavelengths of 416, 266, and 208 nm and employed two-photon and three-photon ionization schemes. The binding energy of the 3s Rydberg state was found to be 3.087 +/- 0.005 eV. The degenerate 3p x, y states have binding energies of 2.251 +/- 0.005 eV, and 3p z is at 2.204 +/- 0.005 eV. Using picosecond and femtosecond time-resolved experiments we spectrally and temporally resolved an intricate sequence of energy relaxation pathways leading from the 3p states to the 3s state. With excitation at 5.96 eV, trimethylamine is found to decay from the 3p z state to 3p x, y in 539 fs. The decay to 3s from all the 3p states takes place with a 2.9 ps time constant. On these time scales, trimethylamine does not fragment at the given internal energies, which range from 0.42 to 1.54 eV depending on the excitation wavelength and electronic state.

Ultrafast structural and isomerization dynamics in the Rydberg-exited quadricyclane: norbornadiene system.

The quadricyclane-norbornadiene system is an important model for the isomerization dynamics between highly strained molecules. In a breakthrough observation for a polyatomic molecular system of that complexity, we follow the photoionization from Rydberg states in the time-domain to derive a measure for the time-dependent structural dynamics and the time-evolving structural dispersion even while the molecule is crossing electronic surfaces. The photoexcitation to the 3s and 3p Rydberg states deposits significant amounts of energy into vibrational motions. We observe the formation and evolution of the vibrational wavepacket on the Rydberg surface and the internal conversion from the 3p Rydberg states to the 3s state. In that state, quadricyclane isomerizes to norbornadiene with a time constant of τ(2) = 136(45) fs. The lifetime of the 3p Rydberg state in quadricyclane is τ(1) = 320(31) and the lifetime of the 3s Rydberg state in norbornadiene is τ(3) = 394(32).

Standoff trace chemical sensing via manipulation of excited electronic state lifetimes

We present a technique for standoff trace chemical sensing that is based on the dependence of excited electronic state lifetimes on the amount of internal vibrational energy. The feasibility of the technique is demonstrated using N,N-dimethylisopropylamine (DMIPA). Time-resolved measurements show that the lifetime of the S1 state in DMIPA exponentially decreases with the amount of vibrational energy. This property is employed to acquire molecular spectral signatures. Two laser pulses are used: one ionizes the molecule through the S1 state; the other alters the S1 state lifetime by depositing energy into vibrations. Reduction of the S1 state lifetime decreases ionization efficiency that is observed by probing the laser-induced plasma with microwave radiation.

Excited-state ions in femtosecond time-resolved mass spectrometry: an investigation of highly excited chloroamines.

We have investigated the processes induced by femtosecond laser pulses in chloroamines, with a focus on the generation and observation of a highly reactive radical and on the involvement and general importance of excited-state ions in time-resolved mass spectrometry investigations of gaseous molecules. We have found that 280 nm femtosecond pulses lead to an ultrafast breakage of the N-Cl bond on the repulsive S1 surface, and that resulting radical is long-lived. When exposing the molecule to 420 nm photons a multiphoton ionization takes place to generate ions; these ions can then be excited with a 280 nm photon. The evidence is unambiguous since we observe a distinct temporal evolution of the ion current with no photoelectrons to match. We suggest that the involvement of excited-state ions is a general phenomenon in time-resolved photoionization studies.

Ultrafast Curve Crossing Dynamics through Conical Intersections in Methylated Cyclopentadienes

We explored the curve crossing dynamics of 1,2,3,4-tetramethyl-cyclopentadiene (TMCPD) and 1,2,3,4,5-pentamethyl-cyclopentadiene (PMCPD) upon pi --> pi* excitation to the 1B(2) state using time-resolved, resonance-enhanced multiphoton ionization mass and photoelectron spectroscopy. Upon excitation with a femtosecond laser pulse at 267 nm, the energy relaxation pathway is observed by a time-delayed probe pulse at 400 nm, which ionizes the molecule through Rydberg states that reveal the momentary state of the molecule in the photoelectron spectra. We observe that the initially populated 1B(2) state decays to the 2A(1) surface in 135 fs in TMCPD and 183 fs in PMCPD, followed by a crossing to the ground state 1A(1) surface on 57 and 60 fs time scales for TMCPD and PMCPD, respectively. The spectroscopic signatures of the 2A(1) states are clearly revealed in the two-photon ionization photoelectron spectra. In both systems we observe that the ground states are recovered completely, indicating that no new molecular structures are created on the time scale of the experiment.

Single Shot Electron Diffraction Experiment Using a Sub ps MeV Electron Source

RF guns have been used for many years for injection into storage rings and to drive Free Electron Lasers (FELs). Currently photo-cathode rf guns are the brightest electron sources available for these types of high energy applications. Electrons are accelerated in rf fields greater than 100 MV/m so the beam becomes relativistic in a few cm quickly reducing the space charge force repulsion. A typical beam produced from such a gun is 5 MeV with sub ps pulse length and greater than 10 electrons per bunch. The relatively high beam energy requires several meter drift distance between target and detector but allows single shot diffraction images to be captured with sub ps resolution. The first results from a diffraction experiment using a 160 nm thick Al target will be presented along with the measured gun beam parameters. Microsc Microanal 12(Supp 2), 2006 Copyright 2006 Microscopy Society of America DOI: 10.1017/S1431927606064154 1432 CD