Full control of the orientation of non-symmetric molecules using weak and moderate electric fields.

We investigate the full control over the orientation of a planar non-symmetric molecule by using moderate and weak electric fields. Quantum optimal control techniques allow us to orient any axis of 6-chloropyridazine-3-carbonitrile, which is taken as prototype example here, along the electric field direction. We perform a detailed analysis by exploring the impact on the molecular orientation of the time scale and strength of the control field. The underlying physical phenomena allowing for the control of the orientation are interpreted in terms of the frequencies contributing to the field-dressed dynamics and to the driving field by a spectral analysis.

Molecular influence on nuclear-quadrupole-coupling effects in laser induced alignment.

We computationally studied the effect of nuclear-quadrupole interactions on the field-free impulsive alignment of different asymmetric-top molecules. Our analysis is focused on the influence of the hyperfine- and rotational-energy-level structures. These depend on the number of nuclear spins, the rotational constants, and the symmetry of the tensors involved in the nuclear spin and external field interactions. Comparing the prototypical large-nuclear-spin molecules iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, and 2,5-diiodobenzonitrile, we demonstrate that the magnitude of the hyperfine splittings compared to the rotational-energy splittings plays a crucial role in the spin-rotational dynamics after the laser pulse. Moreover, we point out that the impact of the quadrupole coupling on the rotational dynamics decreases when highly excited rotational states dominate the dynamics.

Observation of Rydberg Blockade Due to the Charge-Dipole Interaction between an Atom and a Polar Molecule.

We demonstrate Rydberg blockade due to the charge-dipole interaction between a single Rb atom and a single RbCs molecule confined in optical tweezers. The molecule is formed by magnetoassociation of a Rb+Cs atom pair and subsequently transferred to the rovibrational ground state with an efficiency of 91(1)%. Species-specific tweezers are used to control the separation between the atom and molecule. The charge-dipole interaction causes blockade of the transition to the Rb(52s) Rydberg state, when the atom-molecule separation is set to 310(40) nm. The observed excitation dynamics are in good agreement with simulations using calculated interaction potentials. Our results open up the prospect of a hybrid platform where quantum information is transferred between individually trapped molecules using Rydberg atoms.

Ultralong-Range Rydberg Bimolecules.

We predict that ultralong-range Rydberg bimolecules form in collisions between polar molecules in cold and ultracold settings. The interaction of Λ-doublet nitric oxide (NO) with long-lived Rydberg NO(nf, ng) molecules forms ultralong-range Rydberg bimolecules with GHz energies and kilo-Debye permanent electric dipole moments. The Hamiltonian includes both the anisotropic charge-molecular dipole interaction and the electron-NO scattering. The rotational constant for the Rydberg bimolecules is in the MHz range, allowing for microwave spectroscopy of rotational transitions in Rydberg bimolecules. Considerable orientation of NO dipole can be achieved. The Rydberg molecules described here hold promise for studies of a special class of long-range bimolecular interactions.

The Effect of Nuclear-Quadrupole Coupling in the Laser-Induced Alignment of Molecules.

We present a theoretical study of the time-dependent laser alignment of molecules taking into account the hyperfine coupling due to nuclear-quadrupole interactions. The coupling of nuclear spins to the overall angular momentum of molecules significantly influences their rotational dynamics. Here, we systematically analyze the impact of the nuclear-quadrupole coupling on the rotational dynamics of the linear and the asymmetric-top diiodobenzene molecule induced by external laser fields. We explore different regimes of pulse shapes and laser-pulse intensities and detail under which conditions the quadrupole coupling cannot be neglected in the description of the laser alignment of molecules.

Time-dependent analysis of the mixed-field orientation of molecules without rotational symmetry.

We present a theoretical study of the mixed-field orientation of molecules without rotational symmetry. The time-dependent one-dimensional and three-dimensional orientation of a thermal ensemble of 6-chloropyridazine-3-carbonitrile molecules in combined linearly or elliptically polarized laser fields and tilted dc electric fields is computed. The results are in good agreement with recent experimental results of one-dimensional orientation for weak dc electric fields [J. L. Hansen, J. Chem. Phys. 139, 234313 (2013)]. Moreover, they predict that using elliptically polarized laser fields or strong dc fields, three-dimensional orientation is obtained. The field-dressed dynamics of excited rotational states is characterized by highly non-adiabatic effects. We analyze the sources of these non-adiabatic effects and investigate their impact on the mixed-field orientation for different field configurations in mixed-field-orientation experiments.

Adiabatic Mixed-Field Orientation of Ground-State-Selected Carbonyl Sulfide Molecules.

A strong adiabatic mixed-field orientation (Nup /Ntot =0.882) of carbonyl sulfide (OCS) molecules in their absolute ground state is experimentally demonstrated. OCS is oriented in a combination of nonresonant laser and static electric fields inside a two-plate velocity map imaging spectrometer. The transition from nonadiabatic to adiabatic orientation for the rotational ground state is studied by varying the applied laser intensity and static electric field. Above static electric field strengths of 10 kV cm-1 and laser intensities of 1011 W cm-2 the observed degree of orientation reaches a plateau. These results are in good agreement with computational solutions of the time-dependent Schrödinger equation.

Two-state wave packet for strong field-free molecular orientation.

We demonstrate strong laser-field-free orientation of absolute-ground-state carbonyl sulfide molecules. The molecules are oriented by the combination of a 485-ps-long nonresonant laser pulse and a weak static electric field. The edges of the laser pulse create a coherent superposition of two rotational states resulting in revivals of strong transient molecular orientation after the laser pulse. The experimentally attained degree of orientation ⟨cosθ⟩≈0.6 corresponds to the theoretical maximum for mixing of the two states. Switching off the dc field would provide the same orientation completely field free.

Controlling magnetic Feshbach resonances in polar open-shell molecules with nonresonant light.

Magnetically tunable Feshbach resonances for polar paramagnetic ground-state diatomics are too narrow to allow for magnetoassociation starting from trapped, ultracold atoms. We show that nonresonant light can be used to engineer the Feshbach resonances in their position and width. For nonresonant field intensities of the order of 10(9) W/cm(2), we find the width to be increased by 3 orders of magnitude, reaching a few Gauss. This opens the way for producing ultracold molecules with sizable electric and magnetic dipole moments and thus for many-body quantum simulations with such particles.

Equilibria and dynamics of two coupled chains of interacting dipoles.

We explore the energy transfer dynamics in an array of two chains of identical rigid interacting dipoles. Varying the distance b between the two chains of the array, a crossover between two different ground-state (GS) equilibrium configurations is observed. Linearizing around the GS configurations, we verify that interactions up to third nearest neighbors should be accounted to accurately describe the resulting dynamics. Starting with one of the GS, we excite the system by supplying it with an excess energy ΔK located initially on one of the dipoles. We study the time evolution of the array for different values of the system parameters b and ΔK. Our focus is hereby on two features of the energy propagation: the redistribution of the excess energy ΔK among the two chains and the energy localization along each chain. For typical parameter values, the array of dipoles reaches both the equipartition between the chains and the thermal equilibrium from the early stages of the time evolution. Nevertheless, there is a region in parameter space (b,ΔK) where even up to the long computation time of this study, the array does neither reach energy equipartition nor thermalization between chains. This fact is due to the existence of persistent chaotic breathers.

Mixed-field orientation of molecules without rotational symmetry.

The mixed-field orientation of an asymmetric-rotor molecule with its permanent dipole moment nonparallel to the principal axes of polarizability is investigated experimentally and theoretically. We find that for the typical case of a strong, nonresonant laser field and a weak static electric field complete 3D orientation is induced if the laser field is elliptically polarized and if its major and minor polarization axes are not parallel to the static field. For a linearly polarized laser field solely the dipole moment component along the most polarizable axis of the molecule is relevant resulting in 1D orientation even when the laser polarization and the static field are nonparallel. Simulations show that the dipole moment component perpendicular to the most-polarizable axis becomes relevant in a strong dc electric field combined with the laser field. This offers an alternative approach to 3D orientation by combining a linearly polarized laser field and a strong dc electric field arranged at an angle equal to the angle between the most polarizable axis of the molecule and its permanent dipole moment.

Making the best of mixed-field orientation of polar molecules: a recipe for achieving adiabatic dynamics in an electrostatic field combined with laser pulses.

We have experimentally and theoretically investigated the mixed-field orientation of rotational-state-selected OCS molecules and achieved strong degrees of alignment and orientation. The applied moderately intense nanosecond laser pulses are long enough to adiabatically align molecules. However, in combination with a weak dc electric field, the same laser pulses result in nonadiabatic dynamics of the mixed-field orientation. These observations are fully explained by calculations employing both adiabatic and nonadiabatic (time-dependent) models.

Chaos and thermalization in a classical chain of dipoles.

We explore the connection between chaos, thermalization, and ergodicity in a linear chain of N interacting dipoles. Starting from the ground state, and considering chains of different numbers of dipoles, we introduce single site excitations with excess energy ΔK. The time evolution of the chaoticity of the system and the energy localization along the chain is analyzed by computing, up to a very long time, the statistical average of the finite-time Lyapunov exponent λ(t) and the participation ratio Π(t). For small ΔK, the evolution of λ(t) and Π(t) indicates that the system becomes chaotic at approximately the same time as Π(t) reaches a steady state. For the largest considered values of ΔK the system becomes chaotic at an extremely early stage in comparison with the energy relaxation times. We find that this fact is due to the presence of chaotic breathers that keep the system far from equipartition and ergodicity. Finally, we show numerically and analytically that the asymptotic values attained by the participation ratio Π(t) fairly correspond to thermal equilibrium.

Analysis of the classical phase space and energy transfer for two rotating dipoles with and without external electric field.

We explore the classical dynamics of two interacting rotating dipoles that are fixed in the space and exposed to an external homogeneous electric field. Kinetic energy transfer mechanisms between the dipoles are investigated by varying both the amount of initial excess kinetic energy of one of them and the strength of the electric field. In the field-free case, and depending on the initial excess energy, an abrupt transition between equipartition and nonequipartition regimes is encountered. The study of the phase space structure of the system as well as the formulation of the Hamiltonian in an appropriate coordinate frame provide a thorough understanding of this sharp transition. When the electric field is turned on, the kinetic energy transfer mechanism is significantly more complex and the system goes through different regimes of equipartition and nonequipartition of the energy including chaotic behavior.

Nonlinear dynamics of atoms in a crossed optical dipole trap.

We explore the classical dynamics of atoms in an optical dipole trap formed by two identical Gaussian beams propagating in perpendicular directions. The phase space is a mixture of regular and chaotic orbits, the latter becoming dominant as the energy of the atoms increases. The trapping capabilities of these perpendicular Gaussian beams are investigated by considering an atomic ensemble in free motion. After a sudden turn on of the dipole trap, a certain fraction of atoms in the ensemble remains trapped. The majority of these trapped atoms has energies larger than the escape channels, which can be explained by the existence of regular and chaotic orbits with very long escape times.