Russell S. Minns

Observation and control of dissociating and autoionizing Rydberg electron wave packets in NO

The dynamics of predissociating Rydberg electron wave packets are observed using the optical Ramsey method. The time-resolved spectra are hydrogenic and are very well modeled by assuming that only one p Rydberg series contributes to the dynamics. This is in contrast with previous observations of autoionizing Rydberg electron wave packets [Phys. Rev. Lett. 83, 2552 (1999)], which show quite dramatic deviations from hydrogenic behavior above the Born–Oppenheimer limit. The origin of these deviations lies in the interplay between electronic and molecular phase. By exploiting these phases we are able to control the ratio of predissociaton to autoionization.

Interfering Rydberg wave packets in Na

This paper presents an experimental and theoretical analysis of quantum interference between Rydberg wave packets in Na. Pairs of phase-locked wave packets manipulate the total orbital angular momentum of Na Rydberg atoms. Initially, the wave packet is composed of a superposition of s and d Rydberg series. Exploitation of the difference between the quantum defects of the two series allows one to predict the phase of the second wave packet required to engineer specific angular momentum compositions within the resultant wave packet. Experimentally, this final quantum state distribution is analysed in the frequency domain using state-selective field ionization and in the time domain using the optical Ramsey method. The theoretical calculations show how the phase difference between pairs of optical pulses is linked to the corresponding Rydberg frequency spectrum, therefore enabling the control of the quantum state composition of the wave packets. Finally, it is shown that by intuitively chirping one of the laser pulses it is possible to compensate for the dispersion of the wave packet and improve the effectiveness of the angular momentum control.

Development of a new photoelectron spectroscopy instrument combining an electrospray ion source and photoelectron imaging

A new apparatus has been constructed that combines electrospray ionization with a quadrupole mass filter, hexapole ion trap, and velocity-map imaging. The purpose is to record photoelectron images of isolated chromophore anions. To demonstrate the capability of our instrument we have recorded the photodetachment spectra of isolated deprotonated phenol and indole anions. To our knowledge, this is the first time that the photodetachment energy of the deprotonated indole anion has been recorded.

Controlling the radial dynamics of Rydberg wavepackets in Xe using phase-locked optical pulse sequences

We employ a sequence of two phase-locked optical pulses, separated by half a classical orbit period, to control the radial dynamics of electron wavepackets in Xe. We eliminate either even or odd principal quantum number states from the wavepacket and distinguish between these systems by looking at the wavepacket spectrum at different partial revivals. The experimentally observed dynamics are compared with calculations based on multichannel quantum defect theory and the observations are interpreted in terms of the time and phase evolution of the population amplitudes of the Rydberg states contributing to the wavepacket.

Ab-Initio Surface Hopping and Multiphoton Ionisation Study of the Photodissociation Dynamics of CS2

New ab initio surface hopping simulations of the excited state dynamics of CS2 including spin-orbit coupling are compared to new experimental measurements using a multiphoton ionisation probe in a photoelectron spectroscopy experiment. The calculations highlight the importance of the triplet states even in the very early time dynamics of the dissociation process and allow us to unravel the signatures in the experimental spectrum, linking the observed changes to both electronic and nuclear degrees of freedom within the molecule.

Probing the structure and dynamics of molecular clusters using rotational wave packets

Rotational wave packets of the weakly bound C(2)H(2)-He complex have been created using impulsive alignment. The coherent rotational dynamics were monitored for 600 ps enabling extraction of a frequency spectrum showing multiple rotational energy levels up to J = 4. spectrum has been combined with ab initio calculations to show that the complex has a highly delocalized structure and is bound only by ca. 7 cm(-1). The experiments demonstrate how highly featured rotational spectra can be obtained from an extremely cold environment where only the lowest rotational energy states are initially populated.

Hydrogen Bonds in Excited State Proton Transfer.

Hydrogen bonding interactions between biological chromophores and their surrounding protein and solvent environment significantly affect the photochemical pathways of the chromophore and its biological function. A common first step in the dynamics of these systems is excited state proton transfer between the noncovalently bound molecules, which stabilizes the system against dissociation and principally alters relaxation pathways. Despite such fundamental importance, studying excited state proton transfer across a hydrogen bond has proven difficult, leaving uncertainties about the mechanism. Through time-resolved photoelectron imaging measurements, we demonstrate how the addition of a single hydrogen bond and the opening of an excited state proton transfer channel dramatically changes the outcome of a photochemical reaction, from rapid dissociation in the isolated chromophore to efficient stabilization and ground state recovery in the hydrogen bonded case, and uncover the mechanism of excited state proton transfer at a hydrogen bond, which follows sequential hydrogen and charge transfer processes.

VUV excitation of a vibrational wavepacket in D2 measured through strong-field dissociative ionization

Femtosecond vacuum ultraviolet pulses from a monochromated high harmonic generation source excite vibrational wavepackets in the

A RAIRS, TPD and femtosecond laser-induced desorption study of CO, NO and coadsorbed CO + NO on Pd(111)

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Measuring a complete reaction coordinate: Windowless observation of the photodissociation dynamics of CS 2

state of D2. The wavepacket motion is measured through strong field ionization into bound and dissociative ion states yielding