Highly Excited States of Small Molecules and Negative Atomic Ions

Excited states of atoms and molecules exhibit a rich array of diverse phenomena. This dissertation examines two exotic states of atoms at such excited levels: Rydberg molecules and atomic negative ions. Rydberg molecules are formed by a Rydberg atom and one or more ground state atoms, and can be highly polar due to their unusual electronic wave functions and enormous bond lengths. This dissertation expands the theory of these molecules by studying the formation and structure of polyatomic molecules, multichannel Rydberg molecules formed from divalent atoms, and spin effects and relativistic interactions. It also details intermolecular forces between Rydberg molecules, their manipulation via external fields, and their dependence on the intricacies of electron-atom scattering. This electron-atom interaction is also the main component of the latter portion of this thesis, which studies doubly excited states of alkali negative ions in very polarizable and nearly degenerate atomic states. Photodetachment of these states reveals electron correlation and long-range forces stemming from their high excitation

Trilobites, butterflies, and other exotic specimens of long-range Rydberg molecules

This Ph.D. tutorial discusses ultra-long-range Rydberg molecules, the exotic bound states of a Rydberg atom and one or more ground state atoms immersed in the Rydberg electron's wave function. This novel chemical bond is distinct from an ionic or covalent bond, and is accomplished by a very different mechanism: the Rydberg electron, elastically scattering off of the ground state atoms, exerts a weak attractive force sufficient to form the molecule in long-range oscillatory potential wells. In the last decade this topic has burgeoned into a vibrant and mature subfield of atomic and molecular physics following the rapidly developing capability of experiment to observe and manipulate these molecules. This tutorial focuses on three areas where this experimental progress has demanded more sophisticated theoretical descriptions: the structure of polyatomic molecules, the influence of electronic and nuclear spin, and the behavior of these molecules in external fields. The main results are a collection of potential energy curves and electronic wave functions which together describe the physics of Rydberg molecules. Additionally, to facilitate future progress in this field, this tutorial provides a general overview of the current state of experiment and theory.Comment: Comments, criticism, suggestions very welcome. PhD Tutorial based on my Dissertatio

Resonant Compton Upscattering in High Field Neutron Stars

The extremely efficient process of resonant Compton upscattering by relativistic electrons in high magnetic fields is believed to be a leading emission mechanism of high field pulsars and magnetars in the production of intense X-ray radiation. New analytic developments for the Compton scattering cross section using Sokolov & Ternov (S&T) states with spin-dependent resonant widths are presented. These new results display significant numerical departures from both the traditional cross section using spin-averaged widths, and also from the spin-dependent cross section that employs the Johnson & Lippmann (J&L) basis states, thereby motivating the astrophysical deployment of this updated resonant Compton formulation. Useful approximate analytic forms for the cross section in the cyclotron resonance are developed for S&T basis states. These calculations are applied to an inner magnetospheric model of the hard X-ray spectral tails in magnetars, recently detected by RXTE and INTEGRAL. Relativistic electrons cool rapidly near the stellar surface in the presence of intense baths of thermal X-ray photons. We present resonant Compton cooling rates for electrons, and the resulting photon spectra at various magnetospheric locales, for magnetic fields above the quantum critical value. These demonstrate how this scattering mechanism has the potential to produce the characteristically flat spectral tails observed in magnetars.Comment: 2 pages, no figures, The proceedings from the Pulsar Conference: Electromagnetic Radiation from Pulsars and Magnetars will be published in the Astronomical Society of the Pacific Conference Serie

Kato's theorem and ultralong-range Rydberg molecules

We consider non-adiabatic coupling in the "trilobite"-like long-range Rydberg molecules created by perturbing degenerate high-$\ell$ Rydberg states with a ground-state atom. Due to the flexibility granted by the high Rydberg level density, the avoided crossings between relevant potential energy curves can become extremely narrow, leading to highly singular non-adiabatic coupling. We find that the gap between the trilobite potential curve and neighboring "butterfly" or "dragonfly" potential curves can even vanish, as in a conical intersection, if the gap closes at an internuclear distance which matches a node of the $s$-wave radial wave function. This is an unanticipated outcome of Kato's theorem

Delocalization in two and three-dimensional Rydberg gases

As was recently shown in Ref. 1, many eigenstates of a random Rydberg gas with resonant dipole-dipole interactions are highly delocalized. Although the high degree of delocalization is generic to various types of power-law interactions and to both two and three-dimensional systems, in their detailed aspects the coherence distributions are sensitive to these parameters and vary dramatically between different systems. We calculate the eigenstates of both two and three-dimensional gases and quantify their delocalization throughout the atoms in the gas using a coherence measure. By contrasting the angular dependence of the dipole-dipole interaction with an isotropic interaction we obtain additional information about the generic physical principles underlying random interacting systems. We also investigate the density of states and microwave absorption spectra to obtain information about the types of measurements where these delocalized states play a role, and to check that these delocalized eigenstates are robust against various types of perturbation