Coherent Phase Control of Internal Conversion in Pyrazine

TL;DR

This study demonstrates the use of shaped ultrafast laser pulses and genetic algorithms to control and understand the internal conversion and ionization dynamics of excited pyrazine molecules, revealing different control mechanisms for early and late target times.

Contribution

It introduces a novel application of feedback-controlled pulse shaping to manipulate molecular internal conversion pathways in pyrazine, distinguishing two different control regimes based on timing.

Findings

Classical rate equations describe ion growth without feedback.

Genetic algorithms can suppress ionization at targeted times.

Different control mechanisms operate for early and late target times.

Abstract

Shaped ultrafast laser pulses were used to study and control the ionization dynamics of electronically excited pyrazine in a pump and probe experiment. For pump pulses created without feedback from the product signal, the ion growth curve (the parent ion signal as a function of pump/probe delay) was described quantitatively by the classical rate equations for internal conversion of the $S_2$ and $S_1$ states. Very different, non-classical behavior was observed when a genetic algorithm (GA) was used to minimize the ion signal at some pre-determined target time, T. Two qualitatively different control mechanisms were identified for early (T$<1.5$ ps) and late (T$>1.5$ ps) target times. In the former case, the ion signal was largely suppressed for $t<T$, while for $t \gg T$ the ion signal produced by the GA-optimized pulse and a transform limited (TL) pulse coalesced. In contrast, for $T>1.5$ ps the ion growth curve followed the classical rate equations for $t<T$, while for $t \gg T$ the quantum yield for the GA-optimized pulse was much smaller than for a TL pulse. We interpret the first type of behavior as an indication that the wave packet produced by the pump laser is localized in a region of the $S_2$ potential energy surface where the vertical ionization energy exceeds the probe photon energy, whereas the second type of behavior may be described by a reduced absorption cross section for $S_0 \rightarrow S_2$ followed by incoherent decay of the excited molecules.