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Journal of Physics B Atomic Molecular and Optical Physics

Classical scaling and the correspondence between the coupled rate equation and molecular dynamics models for the evolution of ultracold neutral plasma

J. P. Morrison, Nicolas Saquet, Edward R. Grant

Published Jan 9, 2012• 13 citations
Publisher

Abstract

Coupled rate equation calculations demonstrate that the variational rate theory models for the three-body electron–electron–ion scattering dynamics associated with ultracold plasma evolution scale with density in accordance with the classical mechanics of a Coulomb system. Completeness of scaling requires a broad domain of Rydberg levels over which a quasi-equilibrium can be established. For given initial conditions, the predicted evolution of electron temperature with time changes with the choice of n max , i.e. the highest Rydberg orbital populated by three-body recombination. But, if the criterion that defines n max scales with density, then the results scale. Molecular dynamics calculations distinguish bound Rydberg states by an electron–ion distance criterion, R max , which is represented in scaled coordinates by R max = r max a ws , where a ws represents the Wigner–Seitz radius and r max is chosen arbitrarily. The rate equation calculations best conform with the output of molecular dynamics simulations for values of n max defined by a thermal criterion, . In a hydrogenic limit, the thermal criterion equates with a scaled distance criterion when r max = Γ e /2, where Γ e = e 2 /4π 0 a ws k B T e describes the degree of electron correlation. Molecular dynamics simulations conventionally attenuate the Coulomb potential by means of a term, C , . Reference to rate equation calculations suggests a connection between the soft-core term, C , and n min , the lowest Rydberg level considered in the relaxation of the plasma to a quasi-steady state.

DOI
10.1088/0953-4075/45/2/025701

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Double-resonant photoexcitation of nitric oxide in a molecular beam creates a dense ensemble of 50f(2) Rydberg states, which evolves to form a plasma of free electrons trapped in the potential well of an NO + space charge. The plasma travels at the velocity of the molecular beam and, on passing through a grounded grid, yields an electron time-of-flight signal that gauges the plasma size and quantity of trapped electrons. This plasma expands at a rate that fits with an electron temperature as low as 5 K, colder than typically observed for atomic ultracold plasmas. The recombination of molecular NO + cations with electrons forms neutral molecules excited by more than twice the energy of the NO chemical bond, and the question arises whether neutral fragmentation plays a role in shaping the redistribution of energy and particle density that directs the short-time evolution from Rydberg gas to plasma. To explore this question, we adapt a coupled rate-equations model established for atomic ultracold plasmas to describe the energy-grained avalanche of electron–Rydberg and electron–ion collisions in our system. Adding channels of Rydberg predissociation and two-body, electron–cation dissociative recombination to the atomic formalism, we investigate the kinetics by which this relaxation distributes particle density and energy over Rydberg states, free electrons and neutral fragments. The results of this investigation point to conditions under which such processes can effect the steady-state temperature of plasma electrons.

arXiv:1103.0053•Journal of Physics B Atomic Molecular and Optical Physics•Sep 14, 2011•27 citations
Coupled rate equation calculations demonstrate that the variational rate theory models for the three-body electron–electron–ion scattering dynamics associated with ultracold plasma evolution scale with density in accordance with the classical mechanics of a Coulomb system. Completeness of scaling requires a broad domain of Rydberg levels over which a quasi-equilibrium can be established. For given initial conditions, the predicted evolution of electron temperature with time changes with the choice of n max , i.e. the highest Rydberg orbital populated by three-body recombination. But, if the criterion that defines n max scales with density, then the results scale. Molecular dynamics calculations distinguish bound Rydberg states by an electron–ion distance criterion, R max , which is represented in scaled coordinates by R max = r max a ws , where a ws represents the Wigner–Seitz radius and r max is chosen arbitrarily. The rate equation calculations best conform with the output of molecular dynamics simulations for values of n max defined by a thermal criterion, . In a hydrogenic limit, the thermal criterion equates with a scaled distance criterion when r max = Γ e /2, where Γ e = e 2 /4π 0 a ws k B T e describes the degree of electron correlation. Molecular dynamics simulations conventionally attenuate the Coulomb potential by means of a term, C , . Reference to rate equation calculations suggests a connection between the soft-core term, C , and n min , the lowest Rydberg level considered in the relaxation of the plasma to a quasi-steady state.
We present a kinetic model based on coupled rate-equation simulations that accounts for state-detailed rate processes in the evolution of a molecular Rydberg gas to plasma. Calculations support a steady-state picture of Rydberg predissociation and its contribution to plasma dissipation. Inelastic collisions of electrons with Rydberg states efficiently transfer energy from and to the thermal bath of free electrons, giving rise to quasi equilibria of relatively high temperature. Dissipative effects that remove low- n population change the time course of this heating. Including statistically sampled channels of Rydberg predissociation with n - and ℓ-dependent lifetimes slows the relaxation to quasi equilibrium and retards the initial electron temperature increase. At later times, the dissociative loss of low- n population displaces this quasi equilibrium leading to continuous electron heating. Dissociation products appear at a rate that is controlled initially by the rate of Rydberg relaxation to quasi equilibrium. Thereafter, the overall rate at which the total dissociation consumes neutral molecules determines the decay rate for all levels. Simulations predict a total predissociation rate that is smaller than the initial rate of direct electron–ion dissociative recombination. At later times, residual predissociation displays an apparent first-order decay with a rate constant that fits well with experimental observations.
Using state-selected double-resonant excitation, we create a Rydberg gas of NO molecules excited to the principal quantum number n = 50 of the f-series converging to the ion rotational level, N(+) = 2. This gas evolves to form an ultracold plasma, which expands under the thermal pressure of its electrons, and dissipates by electron-ion recombination. Under conditions chosen for this experiment, the observed rates of expansion vary with selected plasma density. Electron temperatures derived from these expansion rates vary from T(e) = 12 K for the highest density up to 16 K at four-fold lower density. Over this range, the apparent electron coupling parameter, defined as Γ(e) = e(2)/4πε(0)ak(B)T(e), falls from nearly three to about one. The decay of charged-particle density fits with a kinetic model that includes parallel paths of direct two-body and stepwise three-body dissociative recombination. The overall recombinative decay follows a second-order rate law, with an observed rate constant that fits with established scattering-theory estimates for elementary two-body dissociative recombination. A small residual increase in this rate constant with decreasing charged-particle density suggests a growing importance of the three-body recombination channel under conditions of decreasing electron correlation.
In recent experiments ultracold plasmas were produced by photoionizing small clouds of laser cooled atoms. This paper presents the results of molecular dynamic simulations for the early time evolution of such plasmas. Contrary to earlier speculation, no evidence of strong electron–electron correlations is observed in the simulations even if the initial value of the coupling parameter (Γe=e2/akTe) is much larger than unity. As electron–electron correlations begin to develop, the correlation energy is released to heat the electrons, raising the electron temperature to the point where Γe∼1 and limiting further development of correlation. Further heating of the electrons occurs as a by-product of three-body recombination. When a model of laser cooling is added to the simulation, the formation of strong ion–ion correlation is observed. Contrary to earlier suggestion, the rate of three-body recombination is observed to be in reasonable agreement with the traditional formula, R=3.9×10−9 s−1[n(cm−3)]2[Te(K)]−9/2, but care must be taken to use the correct temporally evolving temperature, Te. The simulations are challenging because it is necessary to follow three-body recombination into weakly bound (high n quasiclassical) Rydberg states, and the time scale for such states is short compared to that for the plasma dynamics. This kind of problem was faced earlier in computational astrophysics when studying binary star formation in globular clusters and the simulation method used here is adapted from such studies.
Ultracold neutral plasmas, created by photoionizing samples of laser-cooled atoms, have well-controlled initial density and temperature parameters. With initial particle peak densities of ~10^15 m^-3, initial ion temperatures in the tens of micro-Kelvin range, and initial electron temperatures with a controllable range of 1-1000 K, these systems provide a means to study otherwise laboratory-inaccessible parameter ranges for plasma research. Furthermore, these plasmas are inhomogeneous, unconfined, and freely expanding into a vacuum. Despite the extraordinarily low electron temperatures, the electron system remains weakly coupled, although the ion system exhibits strong coupling behavior. While the initial electron temperatures are very low in ultracold plasmas, the temperature evolution has only been measured indirectly, in the earliest ~5% of the plasma lifetime, and often with large uncertainties. We present a technique that, with further theoretical support, can provide straightforward temperature measurements throughout the first fifth of the plasma lifetime. By making use of collective modes of the plasma, we fit a model of Tonks-Dattner resonances (electron sound wave propagating in the plasma) to measurements of these resonances and obtain a time-dependent electron temperature measurement for the ultracold plasma. Three-body recombination, a plasma loss process that has a rate scaling with the -9/2 power of the electron temperature, is of obvious interest in these ultracold plasma systems. Several theoretical works have predicted that the three-body recombination rate expression would need to be modified at these low electron temperatures, although the validity of these changes often hinges on the electron system being strongly coupled. We have performed the lowest temperature measurements of three-body recombination rates in a plasma and show that these measurements potentially provide a low-uncertainty means to calculate electron temperatures.
Double-resonant photoexcitation of nitric oxide in a molecular beam creates a dense ensemble of 51f(2) Rydberg states, which evolves to form a plasma of free electrons trapped in the potential well of an NO + spacecharge. The plasma travels at the velocity of the molecular beam, and, on passing through a grounded grid, yields an electron time-of-flight signal that gauges the plasma size and quantity of trapped electrons. This plasma expands at a rate that fits with an electron temperature as low as 5 K. Dissociative recombination of NO + ions with electrons provides the primary dissipation mechanism for the plasma. We have identified three dissociation pathways, and quantified their relative contributions to the measured rate: Two-body dissociative recombination competes with direct three-body recombination to neutral dissociation products, and with a process in which three-body recombination and electron-impact ionization form an equilibrium population of high-Rydberg states that decays by predissociation. Using available collision-theory rate constants for three-body recombination and ionization, together with quantum mechanical estimates of predissociation rates, we predict that the relaxation of the plasma to a high-Rydberg equilibrium outpaces direct three-body dissociative recombination, and, among second-order processes, the rate of two-body electron-cation dissociative recombination substantially exceeds the rate at which the high-Rydberg equilibrium dissociatively relaxes. The rate constant for dissociative recombination extracted from these data conforms with predictions drawn from theory for isolated electron-ion collisions. Methods based on the dissipation of molecular ultracold plasmas may provide a means for estimating rates of dissociative recombination for a variety of complex molecules.
Double-resonant photoexcitation of nitric oxide in a molecular beam creates a dense ensemble of 50f(2) Rydberg states, which evolves to form a plasma of free electrons trapped in the potential well of an NO + space charge. The plasma travels at the velocity of the molecular beam and, on passing through a grounded grid, yields an electron time-of-flight signal that gauges the plasma size and quantity of trapped electrons. This plasma expands at a rate that fits with an electron temperature as low as 5 K, colder than typically observed for atomic ultracold plasmas. The recombination of molecular NO + cations with electrons forms neutral molecules excited by more than twice the energy of the NO chemical bond, and the question arises whether neutral fragmentation plays a role in shaping the redistribution of energy and particle density that directs the short-time evolution from Rydberg gas to plasma. To explore this question, we adapt a coupled rate-equations model established for atomic ultracold plasmas to describe the energy-grained avalanche of electron–Rydberg and electron–ion collisions in our system. Adding channels of Rydberg predissociation and two-body, electron–cation dissociative recombination to the atomic formalism, we investigate the kinetics by which this relaxation distributes particle density and energy over Rydberg states, free electrons and neutral fragments. The results of this investigation point to conditions under which such processes can effect the steady-state temperature of plasma electrons.