Attosecond-Recollision-Controlled Selective Fragmentation of Polyatomic Molecules

Abstract

Control over various fragmentation reactions of a series of polyatomic molecules (acetylene, ethylene, 1,3-butadiene) by the optical waveform of intense few-cycle laser pulses is demonstrated experimentally. We show both experimentally and theoretically that the responsible mechanism is inelastic ionization from inner-valence molecular orbitals by recolliding electron wave packets, whose recollision energy in few-cycle ionizing laser pulses strongly depends on the optical waveform. Our work demonstrates an efficient and selective way of predetermining fragmentation and isomerization reactions in polyatomic molecules on subfemtosecond time scales.

Subfemtosecond steering of hydrocarbon deprotonation through superposition of vibrational modes

“…Few-cycle waveforms with adjustable carrierenvelope-phase (CEP) have permitted control of charge localization in the ionization and dissociation of diatomic molecules on a subfemtosecond timescale [17][18][19][20][21] . The approach has also been successful in altering the yields of ionization and fragmentation in hydrocarbons 13 . Despite its relevance to stereochemistry, that is, the rearrangements of atoms in a molecule, full control of the deprotonation of hydrocarbons, including the directional steering of the emission of the protons, has, however, not been reported.…”

“…Breaking of the hydrogen bonds is one of the most important dynamic reactions in the chemistry related to biology, combustion and catalysis, motivating considerable efforts to monitor and ultimately control the process. It has been studied in great detail, where efficient strong-field-induced proton ejection was reported [7][8][9][10][11][12][13][14] . Dynamic charge localization 11 and concerted fragmentation 12 scenarios were suggested to explain the origin of the high kinetic energies of the ejected protons.…”

Spatial and temporal control of populations, branching ratios, and electronic coherences in LiH by a single one-cycle infrared pulse

“…Opposite Stark shifts of the potential energy curves of electronic states of different polarities as well as multiphoton processes are essential. This mechanism is different from the one reported in [23,24] that involves inelastic recollisions of the outgoing electron with the cation. Using pump pulses of different polarizations with respect to the molecular axis one can create non stationary electronic densities that rotate perpendicular or parallel to the LiH bond.…”

“…Several experimental schemes rely on the CEP phase value of a CEP stable few cycle pulse [17] for tailoring the electric field profile of the pump pulse and controlling electron localization and dissociation. [8,[18][19][20][21][22][23][24][25] Photoinduced coherent electronic dynamics can also be probed using high harmonic generation [13,[26][27][28], transient absorption spectroscopy [29][30][31], time-resolved molecular-frame photoelectron-angular-distribution [32] and attoclock measurements [33,34].…”

The impact of the carrier envelope phase-dependence on system and laser parameters

“…This opens the door to a great variety of new investigations such as time-resolved measurement of electronic processes or precision control of chemical reactions see, e.g., [3,4,5,6,7,8,9]. One of the main new aspects of such few-cycle pulses is that the Carrier Envelope Phase (CEP), i.e.…”