Lifetimes and decay mechanisms of isotopically substituted ozone above the dissociation threshold: matching quantum and classical dynamics.

Energies and lifetimes of vibrational resonances were computed for 18O-enriched isotopologue 50O3 = {16O16O18O and 16O18O16O} of the ozone molecule using hyperspherical coordinates and the method of complex absorbing potential. Various types of scattering resonances were identified, including roaming OO-O rotational states, the series corresponding to continuation of bound vibrational resonances of highly excited bending or symmetric stretching vibrational modes. Such a series become metastable above the dissociation limit. The coupling between the vibrationally excited O2 fragment and rotational roaming gives rise to Feshbach type resonances in ozone. Different paths for the formation and decay of symmetric 16O18O16O and asymmetric species 16O16O18O were also identified. The symmetry properties of the total rovibronic wave functions of the 18O-enriched isotopologues are discussed in the context of allowed dissociation channels.

Bound and autoionizing potential energy curves in the CH molecule.

This article presents a method of computing bound state potential curves and autoionizing curves using fixed-nuclei R-matrix data extracted from the Quantemol-N software suite. It is a method based on two related multichannel quantum-defect theory approaches. One is applying bound-state boundary conditions to closed-channel asymptotic solution matrices, and the other is searching for resonance positions via eigenphase shift analysis. We apply the method to the CH molecule to produce dense potential-curve datasets presented as graphs and supplied as tables in the publication supplement.

Ozone Formation in Ternary Collisions: Theory and Experiment Reconciled.

The present Letter shows that the formation of ozone in ternary collisions O+O_{2}+M-the primary mechanism of ozone formation in the stratosphere-at temperatures below 200 K (for M=Ar) proceeds through a formation of a temporary complex MO_{2}, while at temperatures above ∼700 K, the reaction proceeds mainly through a formation of long-lived vibrational resonances of O_{3}^{*}. At intermediate temperatures 200-700 K, the process cannot be viewed as a two-step mechanism, often used to simplify and approximate collisions of three atoms or molecules. The developed theoretical approach is applied to the reaction O+O_{2}+Ar because of extensive experimental data available. The rate coefficients for the formation of O_{3} in ternary collisions O+O_{2}+Ar without using two-step approximations were computed for the first time as a function of collision energy. Thermally averaged coefficients were derived for temperatures 5-900 K. It is found that the majority of O_{3} molecules formed initially are weakly bound. Accounting for the process of vibrational quenching of the nascent population, a good agreement with available experimental data for temperatures 100-900 K is obtained.

Threshold photodetachment spectroscopy of the astrochemical anion CN.

Threshold photodetachment spectroscopy has been performed on the molecular anion CN- at both 16(1) K and 295(2) K in a 22-pole ion trap and at 295(2) K from a pulsed ion beam. The spectra show a typical energy dependence of the detachment cross section yielding a determination of the electron affinity of CN to greater precision than has previously been known at 31 163(16) cm-1 [3.864(2) eV]. Allowed s-wave detachment is observed for CN-, but the dependence of the photodetachment cross section near the threshold is perturbed by the long-range interaction between the permanent dipole moment of CN and the outgoing electron. Furthermore, we observe a temperature dependence of the cross section near the threshold, which we attribute to a reduction of the effective permanent dipole due to higher rotational excitation at higher temperatures.

Localized and delocalized bound states of the main isotopologue 48O3 and of 18O-enriched 50O3 isotopomers of the ozone molecule near the dissociation threshold.

Knowledge of highly excited rovibrational states of ozone isotopologues is of key importance for modelling the dynamics of exchange reactions, for understanding longstanding problems related to isotopic anomalies of the ozone formation, and for analyses of extra-sensitive laser spectral experiments currently in progress. This work is devoted to new theoretical study of high-energy states for the main isotopologue 48O3 = 16O16O16O and for the family of 18O-enriched isotopomers 50O3 = {16O16O18O, 16O18O16O, 18O16O16O} of the ozone molecule considered using a full-symmetry approach. Energies and wave functions of bound states near the dissociation threshold are computed in hyperspherical coordinates accounting for the permutation symmetry of three identical nuclei in 48O3 and of two identical nuclei in 50O3, using the most accurate potential energy surface available now. The obtained vibrational band centers agree with observed ones with the root-mean-squares deviation of about 1 cm-1, making the results appropriate for assignments and analyses of future experimental spectra. The levels delocalized between the three potential wells of ozone isomers are computed and analyzed. The states situated deep in the three (for 48O3) or two (for 50O3) equivalent potential wells have similar energies with negligible splitting. However, the states situated just below the potential barriers separating the wells, are split due to the tunneling between the wells resulting in the splitting of rovibrational sub-bands. We evaluate the amplitudes of the corresponding effects and consider possible perturbations in vibration-rotation bands due to interactions between three potential wells. Theoretical predictions for the splitting of observable band centers are provided for the first time.

The Role of Ozone Vibrational Resonances in the Isotope Exchange Reaction 16O16O + 18O → 18O16O + 16O: The Time-Dependent Picture.

We consider the time-dependent dynamics of the isotope exchange reaction in collisions between an oxygen molecule and an oxygen atom: 16O16O + 18O → 16O18O + 16O. A theoretical approach using the multiconfiguration time-dependent Hartree method was employed to model the time evolution of the reaction. Two potential surfaces available in the literature were used in the calculations, and the results obtained with the two surfaces are compared with each other as well as with results of a previous theoretical time-independent approach. A good agreement for the reaction probabilities with the previous theoretical results is found. Comparing the results obtained using two potential energy surfaces allows us to understand the role of the reef/shoulder-like feature in the minimum energy path of the reaction in the isotope exchange process. Also, it was found that the distribution of final products of the reaction is highly anisotropic, which agrees with experimental observations and, at the same time, suggests that the family of approximated statistical approaches, assuming a randomized distribution over final exit channels, is not applicable to this case.

Photodetachment spectroscopy of cold trapped NH2- near threshold.

We have studied photodetachment of the amidogen anion NH2- as a function of photon energy near the detachment threshold. The detachment spectrum is obtained over the energy range of 6190-6355 cm-1 from the loss rate of the anions from a cryogenic radiofrequency multipole ion trap. By modeling all accessible rotational state-to-state photodetachment transitions, we can assign rotational state-specific thresholds to the measured spectrum. In this way, we have determined the electron affinity of NH2 to be 6224 ± 1 cm-1.

Rotational Spectroscopy of a Triatomic Molecular Anion.

Rotational transitions of the nonlinear triatomic molecular anion NH_{2}^{-} have been observed by terahertz spectroscopy in a cryogenic radio frequency ion trap. Absorption of terahertz photons has been probed by rotational state-dependent photodetachment of the trapped negative ions near the detachment threshold. Using this two-photon scheme, the two lowest rotational transitions for the asymmetric top rotor NH_{2}^{-} have been found. For the para nuclear spin configuration, the 1_{0}←0_{0} transition frequency was determined to be 933 954(2) MHz, and for the ortho configuration the 1_{+1}←1_{-1} transition frequency was determined to be 447 375(3) MHz. This result appears to preclude the recent tentative assignment of an interstellar absorption feature to NH_{2}^{-}.

Formation of CN

The existence of negative ions in interstellar clouds has been associated for several decades with the process of radiative electron attachment. In this Letter, we report compelling evidence supporting the fact that the radiative attachment of a low-energy electron is inefficient to form the carbon chain anions CN^{-}, C_{3}N^{-}, and C_{5}N^{-} detected in interstellar clouds. The validity of the approach is confirmed by good agreement with experimental data obtained for the inverse photodetachment process, which represents the major cause of anion destruction in interstellar space. As a consequence, we suggest alternative models that could explain the formation of anions.

Theoretical study of radiative electron attachment to CN, C2H, and C4H radicals.

A first-principle theoretical approach to study the process of radiative electron attachment is developed and applied to the negative molecular ions CN(-), C4H(-), and C2H(-). Among these anions, the first two have already been observed in the interstellar space. Cross sections and rate coefficients for formation of these ions by direct radiative electron attachment to the corresponding neutral radicals are calculated. For the CN molecule, we also considered the indirect pathway, in which the electron is initially captured through non-Born-Oppenheimer coupling into a vibrationally resonant excited state of the anion, which then stabilizes by radiative decay. We have shown that the contribution of the indirect pathway to the formation of CN(-) is negligible in comparison to the direct mechanism. The obtained rate coefficients for the direct mechanism at 30 K are 7 × 10(-16) cm(3)/s for CN(-), 7 × 10(-17) cm(3)/s for C2H(-), and 2 × 10(-16) cm(3)/s for C4H(-). These rates weakly depend on temperature between 10 K and 100 K. The validity of our calculations is verified by comparing the present theoretical results with data from recent photodetachment experiments.

Dissociative recombination of highly symmetric polyatomic ions.

A general first-principles theory of dissociative recombination is developed for highly symmetric molecular ions and applied to H(3)O(+) and CH(3)(+), which play an important role in astrophysical, combustion, and laboratory plasma environments. The theoretical cross sections obtained for the dissociative recombination of the two ions are in good agreement with existing experimental data from storage ring experiments.

Geometrical phase driven predissociation: lifetimes of 2 2 A' levels of H3.

We discuss the role of the geometric phase in predissociation dynamics of vibrational states near a conical intersection of two electronic potential surfaces of a D{3h} molecule. We present a method to calculate lifetimes and positions of predissociated vibrational states (Feshbach resonances) for such X3 molecules. The method accounts for the two coupled three-body potential surfaces. As an example, the method is applied to obtain vibrational levels of the 2;{2}A' electronic state of H3. The three-body recombination rate coefficient for the H+H+H-->H{2}+H process is estimated.

Dissociative recombination of H(3)(+) in the ground and excited vibrational states.

The article presents calculated dissociative recombination (DR) rate coefficients for H(3) (+). The previous theoretical work on H(3) (+) was performed using the adiabatic hyperspherical approximation to calculate the target ion vibrational states and it considered just a limited number of ionic rotational states. In this study, we use accurate vibrational wave functions and a larger number of possible rotational states of the H(3) (+) ground vibrational level. The DR rate coefficient obtained is found to agree better with the experimental data from storage ring experiments than the previous theoretical calculation. We present evidence that excited rotational states could be playing an important role in those experiments for collision energies above 10 meV. The DR rate coefficients calculated separately for ortho- and para-H(3) (+) are predicted to differ significantly at low energy, a result consistent with a recent experiment. We also present DR rate coefficients for vibrationally excited initial states of H(3) (+), which are found to be somewhat larger than the rate coefficient for the ground vibrational level.

Triatomic dissociative recombination theory: Jahn-Teller coupling among infinitely many Born-Oppenheimer surfaces.

The coupling of many Rydberg surfaces poses a stringent challenge for theoretical description. Yet simplifications arise because quantum defect ideas can be applied, which circumvents some of the usual difficulties that arise. We describe a theoretical technique capable of handling these complex interactions, which has already been applied with success to the dynamics of H3 Rydberg states. The extensions necessary to treat the other isotopomers H2D+ and HD2+ are then discussed, along with a preliminary application.

Multichannel cold collisions between metastable Sr atoms.

We present a multichannel-scattering calculation of elastic and inelastic cold collisions between two low-field seeking, metastable 88Sr [(5s5p)3P2] atoms in the presence of an external magnetic field. The scattering physics is governed by strong anisotropic long-range interactions, which lead to pronounced coupling among the partial waves of relative motion. As a result, nonadiabatic transitions are shown to trigger a high rate of inelastic losses. At relatively high energies, T>100 microK, the total inelastic collision rate is comparable with the elastic rate. However, at lower collisional energy, the elastic rate decreases, and at T approximately 1 microK, it becomes substantially smaller than the inelastic rate. Our study suggests that magnetic trapping and evaporative cooling of 88Sr [(5s5p)3P2] atoms, as well as 40Ca [(4s4p)3P2], in low-field seeking states will prove difficult to achieve experimentally.

Theory of dissociative recombination of d(3h) triatomic ions applied to h+3.

We propose a fully quantal description of H+3 dissociative recombination. The new method combines multichannel quantum defect theory, the adiabatic hyperspherical approach, and the techniques of outgoing-wave Siegert pseudostates. The vibrational, rotational, nuclear spin degrees of freedom of the ion, in their full dimensionality, are all taken into account for the first time in any calculation of polyatomic dissociative recombination. Our calculation of the recombination rate confirms that the Jahn-Teller effect is responsible for the large rate in H+3. The resulting theoretical rates for dissociative recombination of H+3 are in good general agreement with experiment.