The Huggins band of ozone is investigated by means of dynamics calculations using a new (diabatic) potential energy surface for the 3 (1)A'(1B2) state. The good overall agreement of the calculated spectrum of vibrational energies and intensities with the experimental spectrum, especially at low to intermediate excitation energies, is considered as evidence that the Huggins band is due to the two C(s) potential wells of the 1B2 state rather than the single C2v well of the 2 (1)A'(1A1) state. The vibrational assignment of the "cold bands," based on the nodal structure of wave functions, on the whole supports the most recent experimental assignment [J. Chem. Phys. 115, 9311 (2001)]. The quantum mechanical spectrum is analyzed in terms of classical periodic orbits and the structure of the classical phase space.
A trajectory method of calculating tunneling probabilities from phase integrals along straight line tunneling paths, originally suggested by Makri and Miller [J. Chem. Phys. 91, 4026 (1989)] and recently implemented by Truhlar and co-workers [Chem. Sci. 5, 2091 (2014)], is tested for one- and two-dimensional ab initio based potentials describing hydrogen dissociation in the 1B1 excited electronic state of pyrrole. The primary observables are the tunneling rates in a progression of bending vibrational states lying below the dissociation barrier and their isotope dependences. Several initial ensembles of classical trajectories have been considered, corresponding to the quasiclassical and the quantum mechanical samplings of the initial conditions. It is found that the sampling based on the fixed energy Wigner density gives the best agreement with the quantum mechanical dissociation rates.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTwo-Dimensional Tunneling: Bifurcations and Competing TrajectoriesV. A. Benderskii, S. Yu. Grebenshchikov, E. V. Vetoshkin, G. V. Mil'nikov, and D. E. MakarovCite this: J. Phys. Chem. 1994, 98, 13, 3300–3306Publication Date (Print):March 1, 1994Publication History Published online1 May 2002Published inissue 1 March 1994https://pubs.acs.org/doi/10.1021/j100064a010https://doi.org/10.1021/j100064a010research-articleACS PublicationsRequest reuse permissionsArticle Views107Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access options Get e-Alerts
The exchange reaction O16+18O2→16O18O+18O and, in particular, its dependence on the transition state region is investigated by classical trajectories on three potential energy surfaces, all based on high-level electronic structure calculations. The first one is the original potential recently constructed by Siebert, Schinke, and Bittererová [Phys. Chem. Chem. Phys. 3, 1795 (2001)]; it has a very small barrier above the O+O2 asymptote. The second potential is a modification of the first one in that the transition state region is adjusted according to new electronic structure calculations on higher levels of theory; it has a small barrier below the asymptote. The third potential is obtained by artificially removing this barrier. The variation of the exchange reaction cross section with collision energy and the magnitude of the thermal rate constant at and below room temperature depend drastically on the shape of the potential at intermediate distances. The second potential, which is believed to represent the transition state structure of the true ground-state potential of ozone best, yields a reaction rate for room temperature that is about a factor of three smaller than the experimental rate. The neglect of nonadiabatic transitions between the several electronic states in the entrance channel may explain this discrepancy. The very slight negative temperature dependence found in the calculations is caused by the strong decrease of the reaction cross section with the initial rotational excitation of the oxygen molecule. Statistical calculations give poor agreement with the classical energy and initial-state dependent cross sections. Nevertheless, the statistical thermal rates are in fair agreement with the classical ones, because the overestimation of the cross sections for low j’s and the underestimation for high j’s partly compensate.
Photodissociation of ozone in the near UV is studied quantum mechanically in two excited electronic states coupled at a conical intersection located outside the Franck-Condon zone. The calculations, performed using recent ab initio PESs, provide an accurate description of the photodissociation dynamics across the Hartley/Huggins absorption bands. The observed photofragment distributions are reproduced in the two electronic dissociation channels. The room temperature absorption spectrum, constructed as a Boltzmann average of many absorption spectra of rotationally excited parent ozone, agrees with experiment in terms of widths and intensities of diffuse structures. The exit channel conical intersection contributes to the coherent broadening of the absorption spectrum and directly affects the product vibrational and translational distributions. The photon energy dependences of these distributions are strikingly different for fragments created along the adiabatic and the diabatic paths through the intersection. They can be used to reverse engineer the most probable geometry of the non-adiabatic transition. The angular distributions, quantified in terms of the anisotropy parameter β, are substantially different in the two channels due to a strong anticorrelation between β and the rotational angular momentum of the fragment O2.
The analysis of the total kinetic energy release (TKER) of the photofragments pyrrolyl + H-atom formed in the photodissociation of pyrrole in the low-lying state 1A2(πσ*) is presented. The TKER distributions contain complementary and often more precise information on the fragmentation process than the broad diffuse absorption spectra. The distributions are calculated quantum mechanically for the diabatic state 1A2(πσ*) either isolated or coupled to the ground electronic state at an exit channel conical intersection. The calculations use the novel ab initio quasi-diabatic potential energy matrix constructed in the work of Picconi and Grebenshchikov [J. Chem. Phys. 148, 104103 (2018)]. The approximate overlap integral-based adiabatic mapping approach is introduced with which the quantum mechanical TKER distributions can be efficiently and accurately reproduced. Finally, the calculated TKERs are compared with the experimental results. The main features of the measured vibrationally resolved distributions are reproduced, and the spectral peaks are assigned and interpreted in detail.
Product imaging of O((3)P2) following dissociation of ozone has been used to determine the relative yields of the product channels O((3)P2) + O2(X (3)Σg(-)) of ozone. All three channels are prominent at all wavelengths investigated. O2 vibrational distributions for each channel and each wavelength are also estimated assuming Boltzmann rotational distributions. Averaged over wavelength in the measured range, the yields of the O((3)P2) + O2(X (3)Σg(-)), O((3)P2) + O2(a (1)Δg), and O((3)P2) + O2(b (1)Σg(+)) channels are 0.36, 0.31,and 0.34, respectively. Photofragment distributions in the spin-allowed channel O((3)P) + O2(X (3)Σg(-)) are compared with the results of quantum mechanical calculations on the vibronically coupled PESs of the singlet states B (optically bright) and R (repulsive). The experiments suggest that considerably more vibrational excitation and less rotational excitation occur than predicted by the quantum calculations. The rotational distributions, adjusted to fit the experimental images, suggest that the dissociation takes place from a more linear configuration than the Franck-Condon bending angle of 117°. The dissociation at most wavelengths results in a positive value of the anisotropy parameter, β, both in the experiment and in the calculations. Calculations indicate that both nonadiabatic transitions and intersystem crossings substantially reduce β below the nominal value of 2.
