Hyperfine-Structure-Induced Depolarization of Impulsively Aligned I_{2} Molecules.

A moderately intense 450 fs laser pulse is used to create rotational wave packets in gas phase I_{2} molecules. The ensuing time-dependent alignment, measured by Coulomb explosion imaging with a delayed probe pulse, exhibits the characteristic revival structures expected for rotational wave packets but also a complex nonperiodic substructure and decreasing mean alignment not observed before. A quantum mechanical model attributes the phenomena to coupling between the rotational angular momenta and the nuclear spins through the electric quadrupole interaction. The calculated alignment trace agrees very well with the experimental results.

Rotational dissociation of impulsively aligned van der Waals complexes.

The nonadiabatic alignment dynamics of weakly bound molecule-atom complexes, induced by a moderately intense 300 fs nonresonant laser pulse, is calculated by direct numerical solution of the time-dependent Schrödinger equation. Our method propagates the wave function according to the coupled channel equations for the complex, which can be done in a very efficient and stable manner out to large times. We present results for two van der Waal complexes, CS2-He and HCCH-He, as respective examples of linear molecules with large and small moments of inertia. Our main result is that at intensities typical of nonadiabatic alignment experiments, these complexes rapidly dissociate. In the case of the CS2-He complex, the ensuing rotational dynamics resembles that of isolated molecules, whereas for the HCCH-He complex, the detachment of the He atom severely perturbs and essentially quenches the subsequent rotational motion. At intensities of the laser pulse ≲2.0 × 1012 W/cm2, it is shown that the molecule-He complex can rotate and align without breaking apart. We discuss the implications of our findings for recent experiments on iodine molecules solvated in helium nanodroplets.

Strongly aligned molecules inside helium droplets in the near-adiabatic regime.

Iodine (I2) molecules embedded in He nanodroplets are aligned by a 160 ps long laser pulse. The highest degree of alignment, occurring at the peak of the pulse and quantified by ⟨cos2𝜃2D⟩, is measured as a function of the laser intensity. The results are well described by ⟨cos2𝜃2D⟩ calculated for a gas of isolated molecules each with an effective rotational constant of 0.6 times the gas-phase value and at a temperature of 0.4 K. Theoretical analysis using the angulon quasiparticle to describe rotating molecules in superfluid helium rationalizes why the alignment mechanism is similar to that of isolated molecules with an effective rotational constant. A major advantage of molecules in He droplets is that their 0.4 K temperature leads to stronger alignment than what can generally be achieved for gas phase molecules-here demonstrated by a direct comparison of the droplet results to measurements on a ∼1 K supersonic beam of isolated molecules. This point is further illustrated for a more complex system by measurements on 1,4-diiodobenzene and 1,4-dibromobenzene. For all three molecular species studied, the highest values of ⟨cos2𝜃2D⟩ achieved in He droplets exceed 0.96.

Laser-Induced Rotation of Iodine Molecules in Helium Nanodroplets: Revivals and Breaking Free.

Rotation of molecules embedded in helium nanodroplets is explored by a combination of fs laser-induced alignment experiments and angulon quasiparticle theory. We demonstrate that at low fluence of the fs alignment pulse, the molecule and its solvation shell can be set into coherent collective rotation lasting long enough to form revivals. With increasing fluence, however, the revivals disappear-instead, rotational dynamics as rapid as for an isolated molecule is observed during the first few picoseconds. Classical calculations trace this phenomenon to transient decoupling of the molecule from its helium shell. Our results open novel opportunities for studying nonequilibrium solute-solvent dynamics and quantum thermalization.