Rotational Coherence and a Sudden Breakdown in Linear Response Seen in Room-Temperature Liquids

Highly energized molecules normally are rapidly equilibrated by a solvent; this finding is central to the conventional (linear-response) view of how chemical reactions occur in solution. However, when a reaction initiated by 33-femtosecond deep ultraviolet laser pulses is used to eject highly rotationally excited diatomic molecules into alcohols and water, rotational coherence persists for many rotational periods despite the solvent. Molecular dynamics simulations trace this slow development of molecular-scale friction to a clearly identifiable molecular event: an abrupt liquid-structure change triggered by the rapid rotation. This example shows that molecular relaxation can sometimes switch from linear to nonlinear response.