No Arabic abstract
Iodine (I$_2$) 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 $langle cos^2 theta_{2D} rangle$, is measured as a function of the laser intensity. The results are well described by $langle cos^2 theta_{2D} rangle$ 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 $sim$ 1 K supersonic beam of isolated molecules. This point is further illustrated for more complex system by measurements on 1,4-diiodobenzene and 1,4-dibromobenzene. For all three molecular species studied the highest values of $langle cos^2 theta_{2D} rangle$ achieved in He droplets exceed 0.96.
Rotation of molecules embedded in He 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 He shell. Our results open novel opportunities for studying non-equilibrium solute-solvent dynamics and quantum thermalization.
Dimers and trimers of carbonyl sulfide (OCS) molecules embedded in helium nanodroplets are aligned by a linearly polarized 160 ps long moderately intense laser pulse and Coulomb exploded with an intense 40 fs long probe pulse in order to determine their structures. For the dimer, recording of 2D images of OCS$^+$ and S$^+$ ions and covariance analysis of the emission directions of the ions allow us to conclude that the structure is a slipped-parallel shape similar to the structure found for gas phase dimers. For the trimer, the OCS$^+$ ion images and corresponding covariance maps reveal the presence of a barrel-shaped structure (as in gas phase) but also other structures not present in the gas phase, most notably a linear chain structure.
We combine experimental and theoretical approaches to explore excited rotational states of molecules embedded in helium nanodroplets using CS$_2$ and I$_2$ as examples. Laser-induced nonadiabatic molecular alignment is employed to measure spectral lines for rotational states extending beyond those initially populated at the 0.37 K droplet temperature. We construct a simple quantum mechanical model, based on a linear rotor coupled to a single-mode bosonic bath, to determine the rotational energy structure in its entirety. The calculated and measured spectral lines are in good agreement. We show that the effect of the surrounding superfluid on molecular rotation can be rationalized by a single quantity -- the angular momentum, transferred from the molecule to the droplet.
Much of our knowledge about dynamics and functionality of molecular systems has been achieved with femtosecond time-resolved spectroscopy. Despite extensive technical developments over the past decades, some classes of systems have eluded dynamical studies so far. Here, we demonstrate that superfluid helium nanodroplets, acting as thermal bath of 0.4 K temperature to stabilize weakly bound or reactive systems, are well suited for time-resolved studies of single molecules solvated in the droplet interior. By observing vibrational wavepacket motion of indium dimers (In$_2$) for over 50 ps, we demonstrate that the perturbation imposed by this quantum liquid can be lower by a factor of 10-100 compared to any other solvent, which uniquely allows to study processes depending on long nuclear coherence in a dissipative environment. Furthermore, tailor-made microsolvation environments inside droplets will enable to investigate the solvent influence on intramolecular dynamics in a wide tuning range from molecular isolation to strong molecule-solvent coupling.
Quantum pumping, in its different forms, is attracting attention from different fields, from fundamental quantum mechanics, to nanotechnology, to superconductivity. We investigate the crossover of quantum pumping from the adiabatic to the anti-adiabatic regime in the presence of dissipation, and find general and explicit analytical expressions for the pumped current in a minimal model describing a system with the topology of a ring forced by a periodic modulation of frequency omega. The solution allows following in a transparent way the evolution of pumped DC current from much smaller to much larger omega values than the other relevant energy scale, the energy splitting introduced by the modulation. We find and characterize a temperature-dependent optimal value of the frequency for which the pumped current is maximal.