The past three decades have seen extraordinary progress in the manipulation of neutral atoms with laser light, to the point where it is now routine to trap and cool both individual atoms and entire atomic clouds to temperatures of only a few tens of nanoKelvin in a controlled and repeatable fashion. In this thesis we study several applications of Rydberg atoms – atoms with an electron in a highly excited state – within such ultracold atomic systems. Due to their highly-excited electron, Rydberg atoms have a number of exaggerated properties: in addition to being physically large, they have long radiative lifetimes, and interact strongly both with one another and with applied external fields. Rydberg atoms consequently find many interesting applications within ultracold atomic physics. We begin this thesis by analysing the way in which a rubidium atom prepared in an excited Rydberg state decays to the ground state. Using quantum defect theory to model the wavefunction of the excited electron, we compute branching ratios for the various decay channels that lead out of the Rydberg states of rubidium. By using these results to carry out detailed simulations of the radiative cascade process, we show that the dynamics of spontaneous emission from Rydberg states cannot be adequately described by a truncated atomic level structure. We then investigate the stability of ultra-large diatomic molecules formed by pairs of Rydberg atoms. Using quantum defect theory to model the electronic wavefunctions, we apply molecular integral techniques to calculate the equilibrium distance and binding energy of these molecular Rydberg states. Our results indicate that these Ryberg macro-dimers are predicted to show a potential minimum, with equilibrium distances of up to several hundred nanometres. In the second half of this thesis, we present a new method of symbolically evaluating functions of matrices. This method, which we term the method of path-sums, has applications to the simulation of strongly-correlated many-body Rydberg systems, and is based on the combination of a mapping between matrix multiplications and walks on weighted directed graphs with a universal result on the structure of such walks. After presenting and proving this universal graph theoretic result, we develop the path-sum approach to matrix functions. We discuss the application of path-sums to the simulation of strongly-correlated many-body quantum systems, and indicate future directions for the method.
The past three decades have seen extraordinary progress in the manipulation of neutral atoms with laser light, to the point where it is now routine to trap and cool both individual atoms and entire atomic clouds to temperatures of only a few tens of nanoKelvin in a controlled and repeatable fashion. In this thesis we study several applications of Rydberg atoms – atoms with an electron in a highly excited state – within such ultracold atomic systems. Due to their highly-excited electron, Rydberg atoms have a number of exaggerated properties: in addition to being physically large, they have long radiative lifetimes, and interact strongly both with one another and with applied external fields. Rydberg atoms consequently find many interesting applications within ultracold atomic physics. We begin this thesis by analysing the way in which a rubidium atom prepared in an excited Rydberg state decays to the ground state. Using quantum defect theory to model the wavefunction of the excited electron, we compute branching ratios for the various decay channels that lead out of the Rydberg states of rubidium. By using these results to carry out detailed simulations of the radiative cascade process, we show that the dynamics of spontaneous emission from Rydberg states cannot be adequately described by a truncated atomic level structure. We then investigate the stability of ultra-large diatomic molecules formed by pairs of Rydberg atoms. Using quantum defect theory to model the electronic wavefunctions, we apply molecular integral techniques to calculate the equilibrium distance and binding energy of these molecular Rydberg states. Our results indicate that these Ryberg macro-dimers are predicted to show a potential minimum, with equilibrium distances of up to several hundred nanometres. In the second half of this thesis, we present a new method of symbolically evaluating functions of matrices. This method, which we term the method of path-sums, has applications to the simulation of strongly-correlated many-body Rydberg systems, and is based on the combination of a mapping between matrix multiplications and walks on weighted directed graphs with a universal result on the structure of such walks. After presenting and proving this universal graph theoretic result, we develop the path-sum approach to matrix functions. We discuss the application of path-sums to the simulation of strongly-correlated many-body quantum systems, and indicate future directions for the method.
In this thesis I present several theoretical methods to explore the excitation dynamics of Ultracold Rydberg systems in various regimes. For some applications the details of interactions between Rydberg atoms have to be carefully examined, while for others, the many-body aspect of Rydberg excitation may be crucial. In both cases, the basic prerequisite is to know the interactions sufficiently well. I will review the basic concepts how to evaluate molecular potentials in various Hund's cases and approximations. Long-range Rydberg-Rydberg interactions between Rydberg atoms induce ℓ-mixing which in certain situations gives rise to molecular resonances. For these resonances, we calculate long-range potentials in Hund's case (c) by diagonalization of an interaction matrix. The excitation dynamics of the resonances is always modeled as pair excitation. At high principal quantum number n, the interactions between Rydberg atoms can blockade the excitation of many surrounding atoms in the range of few μm. The atoms within this range are strongly correlated so that many-body treatments are, in general, needed. To describe this blockading effect and other manifestations of the collective behavior of Rydberg excitation, such as the many-body Rabi oscillations, spatial correlations between atoms and the fluctuations of the number of excited atoms, I have used three different approaches. In the mean-field approach the interactions between different atoms is modeled by a distribution of mean-field shifts for which a distribution of probabilities is calculated, A good agreement between the theoretical model and experimental measurements is found. To study the correlations between atoms the many-body wavefunction is numerically computed. The possibility of observing the many-body Rabi oscillations of Rydberg excitation and other aspects of many-body dynamics is analyzed. Although strong interactions cannot be treated perturbatively other expansions may be feasible. I will show that the expansion in powers of the single atom Rabi frequency can be evaluated in the interaction and Heisenberg picture. The expansion is expected to behave well for arbitrary strong interactions. ^
This thesis is a theoretical study of the behavior of electrons in atoms and molecules subjected to external electromagnetic fields. Three electronic systems have been central in this work, the atomic and quasimolecular Rydberg states and the carbon allotrope graphene. The exaggerated properties of the highly excited Rydberg atoms, such as long lifetime, large spatial extension and low binding energy make them excellent candidates for both theoretical and experimental considerations. The analytical solutions of the hydrogen atom in quantum mechanics provide a good description for most Rydberg atoms. This is exploited in the work presented in this thesis and the accompanying papers, where we show results of numerical computations on interacting Rydberg atoms, with and without the presence of radiating fields, as well as dynamic Rydberg wave packets influenced by a train of femtosecond laser pulses. In the final part of the thesis the optical process of high-order harmonic generation in an extended molecular structure, represented by graphene, is considered. Rydberg atoms have a large dipole moment due to the large average electronic radius in the atom, which leads to a very strong dipole-dipole coupling between interacting particles in a gas of cold Rydberg atoms. This interaction, which is dependent on the internuclear separation between the atoms, induces a shift in the energy levels, which again prohibits the excitation of more than one atom in the gas, an effect commonly known as the Rydberg blockade. A correlated behavior is observed for the intrashell transitions in mutually excited Rydberg atoms. The microwave field driven dynamics is significantly supressed for internuclear distances below a given conditional radius which scales linearly with the principal quantum number n. Such an entangled electronic behavior may open for the realization of quantum gates applied in quantum informatics. The long-range interaction of Rydberg atoms is dominated by the dipole-dipole terms. Nevertheless, the investigation of two interacting Rydberg atoms, without the influence of electromagnetic radiation, has shown that the lower order multipolar terms play a vital role in the energy shifts as well as for the electronic probability distributions. We found that the energy curves, when including all multipole orders, correspond to both repulsive and attractive states with a stronger repulsion than attraction. We also propose a laser assisted approach for stabilization of Rydberg gases by controlled transitions between such attractive and repulsive energy states. Single-electron ionization of a dynamic Rydberg wave packet confined within a single energy level has been investigated. The ionization probability of an intrashell Rydberg wave packet depends strongly on the degree of polarization. For a wave packet driven repeatedly between the circular (least polarized) state and the linear (most polarized) state by a rotating microwave field and subjected to a train of femtosecond laser pulses, the ionization probability will depend crucially on the laser repetition rate and number of pulses. The angular-resolved ionization probability and energy distribution in the continuum are also influenced by these parameters. The last part of the thesis is devoted to the study of high-order harmonic generation (HHG) in graphene. In the simple man’s model HHG can be described by an electron that is ionized and driven in an external field, after which it returns to the parent atom and recombines, emitting a high-energy photon with frequency that is a multiple of the incident laser frequency. We show that the harmonic spectra obtained from the interaction with linearly as well as circularly polarized femtosecond lasers yield harmonics up the classical limit for extended molecules. In contrast to diatomic molecules, the stable grid structure of graphene ensures that the harmonic generation cutoff remains constant with increasing signal power as the graphene diameter extends beyond the classical limit. Additionally, for circularly polarized lasers harmonics exceeding the classical predictions have been observed.
The work presented in this dissertation represents a comprehensive study on long-range interactions between alkali Rydberg atoms. As a consequence of their size, Rydberg atoms possess very large dipole moments, making them highly sensitive to external fields and to other Rydberg atoms. The strong dipole-dipole interaction between two Rydberg atoms results in a mixing of their angular momentum characters, which is the cornerstone of the work presented here. We describe the ℓ-mixing between various local molecular asymptotes through a residual Coulomb potential, assuming no electron cloud overlap. We then directly diagonalize an interaction Hamiltonian consisting of these Rydberg-Rydberg interactions and spin-orbit (fine structure) coupling in the Hund's case (c). In this manner, we calculate potential energy curves for various molecular symmetries and find that some of these curves exhibit deep potential wells, capable of supporting very extended bound molecular states ( macrodimers). We analyze the specific structure of the ℓ-mixing for these potential wells and derive convenient n-scaling relations for both their equilibrium separations Re and well depths De. We also explore various properties of the macrodimers, including their response to small electric fields and stability with respect to predissociation. We note throughout the dissertation that the detection of such extended dimers could help progress studies in a variety of areas such as exotic, ultracold chemistry and quantum information and computing. To facilitate detection, we propose a scheme to form and study the macrodimers via photoassociation (PA). We present calculated PA lineshapes from two different electronic ground states based on a harmonic trapping model. We find that both PA signals vary significantly with the laser detunings, indicating that different ℓ-characters could be probed at different equilibrium lengths. Finally, we extend the two-body formalism to the case of three interacting Rydberg atoms and present preliminary results for triply excited 58p rubidium atoms along a common axis. We provide a few examples of surface plots corresponding to different local asymptotes, each with a unique three-dimensional "landscape" and discuss the relevance of the physical features. The highlight of our analysis is the appearance of a potential well, which indicates the formation of a linear trimer. ^
Collisions involving Rydberg atoms reveal detailed information on the state of a background medium and can be used as diagnostic probes of temperature and density distributions in a neutral or ionized gas. Spectroscopy of Rydberg atoms in highly excited states reveals the interaction of the Rydberg electron with core electrons, including relativistic effects, and can be used for precise determination of fundamental constants. The advent of ultracold trapping and cooling methods in the last three decades has ushered in a new paradigm in Rydberg physics control and manipulation. The concept of the Rydberg blockade, for instance, al- lows for precise control of long-range dipolar interaction between atoms, creation of correlated many-body wave functions, and realization of macroscopic quantum entanglement and quan- tum logic operations. The formation of a new class of Rydberg molecules arising from ground and Rydberg atom collisions can be used to manipulate electron-atom scattering phase shifts, form and manipulate molecules with enormous permanent electric dipole moments, study Ry- dberg chemistry at the ultracold, and realize macroscopic quantum polaronic systems. In this thesis, I will investigate charge transfer from covalent ground-Rydberg collisions to form heavy ion pair states. In another related study, I explore the formation of spin-mixed ultralong range Rydberg molecules, by accounting for spin-dependent relativistic fine and hyperfine interac- tion. Such studies help to not only explain experimental observations, but also point to how molecular reactions can be controlled using small electric or magnetic fields.
Optical lattices make it possible to trap and coherently control large ensembles of ultracold atoms. They provide the possibility to create lattice potentials that mimic the structure of solid-state systems, and to control these potentials dynamically. In this thesis, we study how dynamical manipulations of the lattice geometry can be used to perform different tasks, ranging from quantum information processing to the creation of diatomic molecules. We first examine the dynamical properties of ultracold atoms trapped in a lattice whose periodicity is dynamically doubled. We derive a model describing the dynamics of the atoms during this process, and compute the different interaction parameters of this model. We investigate different ways of using this lattice manipulation to optimise the initialisation time of a Mott-insulating state with one atom per site, and provide a scaling law related to the interaction parameters of the system. We go on to show that entangling operations between the spin of adjacent atoms are realisable with optical lattices forming arrays of double-well potentials. We study the creation of a lattice containing a spin-encoded Bell-pair in each double-well, and show that resilient, highly-entangled many-body states are realisable using lattice manipulations. We show that the creation of cluster-like states encoded on Bell-pairs can be achieved using these systems, and we provide measurement networks that allow the execution of quantum algorithms while maintaining intact the resilience of the system. Finally, we investigate the possibility to create a diatomic molecular state and simulate Fermi systems via the excitation to Rydberg levels of ground-state atoms trapped in optical lattices. We develop a method based on symbolical manipulations to compute the interaction parameters between highly-excited electrons, and evaluate them for different electronic configurations. We use these parameters to investigate the existence of diatomic molecular states with equilibrium distances comparable to typical lattice spacings. Considering the possibility to excite atoms trapped in an optical lattice to Rydberg levels such that the electronic cloud of neighbouring atoms overlap, we propose a model describing their interactions and compute its parameters. If such systems were realised, they would allow the simulation of Fermi systems at a temperature much below the Fermi temperature, thus enabling the observation of quantum phenomena hitherto inaccessible with current technology.
Recent achievements in ultra-cold experiments have made quantum simulation of interacting many-body systems possible in a well controllable environment. Of many candidates as quantum simulators, Rydberg atoms have been extensively utilised due to its exaggerated and fascinating atomic properties. Example includes high susceptibility to electric fields and relatively long life time in comparison to atoms in low-lying states. The tunable interaction between Rydberg atoms have made them even more versatile in simulating quantum many-body systems, e.g. interacting spin-1/2 particles. We will start the thesis by reviewing these properties of Rydberg atoms and explain how they lead to the Rydberg lattice gases that of interest. Following the review of the essential knowledge of Rydberg atoms, we first study the ground states of interacting Rydberg lattice gases in both one-dimension and two-dimensions. The many-body system we are interested in is initially prepared in a Mott-insulator state, with each lattice site containing one atom that is laser coupled to its highly excited Rydberg state. The extremely huge van der Waals interactions between Rydberg atoms at close distance leads to an interesting Rydberg blockade effect. As we shall show, these strong interactions lead to rich phases and critical behaviours in the ground states of the many-body Hamiltonians that describes the systems. The aim of the first three chapters is to analyse these ground states in detail. Having investigated the static properties, we then move on to study the dynamical behaviour of a class of generic spin models which can in principal be realised by Rydberg lattice gases with tunable blockade radius. By deriving an effective master equation, and comparing it to the exact calculation, we will demonstrate how different pure initial states eventually evolve to the same equilibrium state and analysed in detail the time evolution and the steady state.