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International Symposium on Molecular Spectroscopy (ISMS)

EFFECTIVE ION-IN-MOLECULE POTENTIALS FOR NON-PENETRATING RYDBERG STATES OF POLAR MOLECULES

Stephen L. Coy, Bryan M. Wong, Robert W. Field, Yan Zhou, David Grimes

Published Jun 23, 2015• 0 citations
Publisher

Abstract

Rydberg states of atoms or molecules for which the inner turning point of the Rydberg electron on the radial plus centrifugal potential lies outside the bulk of the ion core electron density are known as core-non-penetrating states. Interpretation of Rydberg spectroscopic data for polar molecules makes use of effective potentials that include ionic bonding and polarizability in order to represent electric properties of the ion core. We examine the accuracy and convergence properties of single-center polarization potentials and show that the center of charge representation, for which the core dipole moment is zero so that first-order l-mixing can be neglected, is excluded by the convergence sphere for use with l-states that can be treated by an expansion about the center or mass, the center of dipole or a newly-defined center of polarizability. The potential expansion converges only outside a sphere enclosing the charge distribution, and the sphere is much larger when the center of charge is used. For higher l-states of the rotating molecule (turning points defined in center of mass), the sphere required for convergence is much smaller for an origin within the charge distribution, so that lower l states are modeled correctly.

DOI
10.15278/isms.2015.tj08

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Rydberg states of atoms or molecules for which the inner turning point of the Rydberg electron on the radial plus centrifugal potential lies outside the bulk of the ion core electron density are known as core-non-penetrating states. Interpretation of Rydberg spectroscopic data for polar molecules makes use of effective potentials that include ionic bonding and polarizability in order to represent electric properties of the ion core. We examine the accuracy and convergence properties of single-center polarization potentials and show that the center of charge representation, for which the core dipole moment is zero so that first-order l-mixing can be neglected, is excluded by the convergence sphere for use with l-states that can be treated by an expansion about the center or mass, the center of dipole or a newly-defined center of polarizability. The potential expansion converges only outside a sphere enclosing the charge distribution, and the sphere is much larger when the center of charge is used. For higher l-states of the rotating molecule (turning points defined in center of mass), the sphere required for convergence is much smaller for an origin within the charge distribution, so that lower l states are modeled correctly.
High Rydberg states about a dipolar molecular core can exhibit special features due to the exceptionally long range of the electrical anisotropy of the core. Unlike all other, more localized, couplings of the Rydberg electron to the ion, here the interaction is not shielded by the centrifugal barrier. The influence of the core even on states of the electron with higher angular momentum l and the significant matrix elements between states that differ considerably in the principal quantum number n make this problem worthy of separate considerations. Using specialized computational techniques (both analytical and numerical) for the exact evaluation of the relevant matrix elements, the role of both inter- and intra-Rydberg series coupling is discussed. The importance of the latter (i.e., the coupling of the Rydberg electron to the rotation of the core) is emphasized. Special attention is given to the role of an external dc electrical field that is different in the present problem in that it does not significantly dilute the strength of the electron-core interaction. A positively charged core can have a dipole moment (defined with respect to its center of mass) larger than that of neutral polar molecules, particularly if the charge is localized. Hence the interseries and intraseries dynamics discussed in this paper can give rise to experimentally measurable special effects. \textcopyright{} 1996 The American Physical Society.
We introduce a computational method developed for study of long-range molecular Rydberg states of such systems that can be approximated by two electrons in a model potential of the atomic cores. Only diatomic molecules are considered. The method is based on a two-electron RRR-matrix approach inside a sphere centered on one of the atoms. The wave function is then connected to a Coulomb region outside the sphere via a multichannel version of the Coulomb Green's function. This approach is put into a test by its application to a study of Rydberg states of the hydrogen molecule for internuclear distances RRR from 20 to 400 bohrs and energies corresponding to nnn from 3 to 22. The results are compared with previous quantum chemical calculations (lower quantum numbers nnn) and computations based on contact-potential models (higher quantum numbers nnn).
"Core nonpenetrating Rydberg states of molecules are a neglected state of matter. They could have a variety of uses, notably state-selective production of molecular ions. Due to the \textit{l}(\textit{l}+1)/r2^{2}2 centrifugal barrier that prevents the Rydberg electron in high-\textit{l} states from penetrating inside of the ion core, the electron is essentially uncoupled from the ion core, and the system becomes atom-like with long lifetimes, an ""almost good"" \textit{l} quantum number, and electronic transitions that follow Δ\DeltaΔJ+^{+}+=0 and Δ\DeltaΔv+^{+}+=0 propensity rules. However, in most molecules access to these states, via a sequence of Δ\DeltaΔ\textit{l}=+1 transitions from low-n*, low-\textit{l} states, is blocked by the necessity to traverse the ""zone of death,"" in which nonradiative decay mechanisms are prohibitively fast. We exploit Chirped Pulse millimeter-Wave (CPmmW) spectroscopy to efficiently excite Ca atoms and BaF molecules to core nonpenetrating states in the absence of nonradiative decay mechanisms. A universal method for preparing core nonpenetrating Rydberg states of molecules, which combines CPmmW spectroscopy with STImulated Raman Adiabatic Passage (STIRAP), will be discussed."
Abstract The results of theoretical studies of the resonant quenching and ion-pair formation processes induced by collisions of Rydberg atoms with highly polar molecules possessing small electron affinities are reported. We elaborate an approach for describing collisional dynamics of both processes and demonstrate the predominant role of resonant quenching channel of reaction for the destruction of Rydberg states by electron-attaching molecules. The approach is based on the solution of the coupled differential equations for the transition amplitudes between the ionic and Rydberg covalent terms of a quasimolecule formed during a collision of particles. It takes into account the possibility of the dipole-bound anion decay in the Coulomb field of the positive ionic core and generalizes previous models of charge-transfer processes involving Rydberg atoms to the cases, when the multistate Landau–Zener approaches become inapplicable. Our calculations for Rb ( nl ) atom perturbed by C 2 H 4 SO 3 , CH 2 CHCN , CH 3 NO 2 , CH 3 CN , C 3 H 2 O 3 , and C 3 H 4 O 3 molecules show that the curves representing the dependence of the resonant quenching cross sections on the principal quantum number n are bell-shaped with the positions of maxima being shifted towards lower values of n and the peak values, σ max ( q ) , several times higher than those for the ion-pair formation, σ max
Rydberg molecule, formed by one or more Rydberg atoms, exhibits remarkable properties, including an exceptionally large spatial extent, rich rovibrational level structures, permanent electric dipole moments, and a pronounced sensitivity to external fields. Based on the underlying binding mechanisms, Rydberg molecules can be divided into three categories, the ground-Rydberg molecule that is bound via a low-energy electron-atom scattering interaction between ground atom and Rydberg electron, the Rydberg-Rydberg molecule that is bound via a long-range electrostatic interaction between Rydberg atoms, and the ion-Rydberg molecule that is bound via single- or multi-polar interactions between Rydberg atom and ion. This review focuses on recent theoretical and experimental advances in diatomic Rydberg molecules, covering their formation and binding mechanisms, potential energy curves, experimental observations, and spectroscopic properties, with the aim of providing a comprehensive overview of the current state and future prospects of this rapidly developing field.