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Chelsea Liekhus-Schmaltz

Publications and source records attributed to Chelsea Liekhus-Schmaltz.

4 recordsLinked to original sources

Strictly Non-Adiabatic Quantum Control of the Acetylene Dication Using an Infrared Field

We demonstrate the existence of a strictly non-adiabatic control pathway in deprotonation of the acetylene dication. This pathway is identified experimentally by measuring a kinetic energy shift in an ion coincidence experiment. We use a TDSE simulation to identify which properties most strongly affect our control. We find that resonant control around conical intersections is limited by the speed of non-adiabatic dynamics.

physics.chem-ph↗

Ultrafast Isomerization in Acetylene Dication: To Be or Not To Be

Experimental evidence has pointed toward the existence of ultrafast proton migration and isomerization as a key process for acetylene and its ions, however the actual mechanism for ultrafast isomerization of the acetylene [HCCH]2+ to vinylidene [H2CC]2+ dication remains nebulous. Theoretical studies show a high potential barrier of over 2eV for the isomerization pathways on the low lying dicationic states, implying that the corresponding isomerization should take picoseconds or even longer according to transition state theory. However a recent experiment at a femtosecond X-ray free electron laser (XFEL) [Nature Commun. 6, 8199 (2015)] suggests that large amplitude hydrogen migration proceeds on a sub-100 femtosecond time scale. In order to resolve the contradiction, we present a complete theoretical study of the dynamics of acetylene dication produced by Auger decay after X-ray photoionization of the carbon atom K shell. We find that isomerization does not occur on the sub-100 fs timescale and is not required to explain the time-resolved Coulomb imaging experiment. This study resolves the seeming contradiction between experiment and theory concerning the isomerization time scale in acetylene dication. This work calls for careful interpretation of structural information from the widely applied Coulomb momentum imaging method but also points out its strengths in mapping out momentum dispersion dynamics even when structural variation is minor.

physics.chem-ph↗

Geometric Dependence of Strong Field Enhanced Ionization in D$_{2}$O

We have studied strong-field enhanced dissociative ionization of D$_{2}$O in 40 fs, 800 nm laser pulses with focused intensities of $< 1 - 3 \times 10^{15}W/cm^2$ by resolving the charged fragment momenta with respect to the laser polarization. We observe dication dissociation into OD$^{+}$/D$^{+}$ dominates when the polarization is out of the plane of the molecule, whereas trication dissociation into O$^{+}$/D$^{+}$/D$^{+}$ is strongly dominant when the polarization is aligned along the D-D axis. Dication dissociation into O/D$^{+}$/D$^{+}$, and O$^{+}$/D$_2$$^{+}$ is not seen, nor is there any significant fragmentation into multiple ions when the laser is polarized along the C$_{2v}$ symmetry axis of the molecule. Even below the saturation intensity for OD$^{+}$/D$^{+}$, the O$^{+}$/D$^{+}$/D$^{+}$ channel has higher yield. By analyzing how the laser field is oriented within the molecular frame for both channels, we show that enhanced ionization is driving the triply charged three body breakup, but is not active for the doubly charged two body breakup. We conclude that laser-induced distortion of the molecular potential suppresses multiple ionization along the C$_{2v}$ axis, but enhances ionization along the D-D direction.

physics.chem-ph↗

Coherent control using kinetic energy and the geometric phase of a conical intersection

Conical intersections (CI) between molecular potential energy surfaces with non-vanishing non-adiabatic couplings generally occur in any molecule consisting of at least three atoms. They play a fundamental role in describing the molecular dynamics beyond the Born-Oppenheimer approximation and have been used to understand a large variety of effects, from photofragmentation and isomerization to more exotic applications such as exciton fission in semiconductors. However, few studies have used the features of a CI as a tool for coherent control. Here we demonstrate two modes of control around a conical intersection. The first uses a continuous light field to control the population on the two intersecting electronic states in the vicinity of a CI. The second uses a pulsed light field to control wavepackets that are subjected to the geometric phase shift in transit around a CI. This second technique is likely to be useful for studying the role of nuclear dynamics in electronic coherence phenomena.

quant-ph↗