A new, global analytical potential energy surface is constructed for the X A8 electronic ground state of HOCl that accurately includes the HClO isomer. The potential is obtained by using accurate ab initio data from a previously published surface @Skokov et al., J. Chem. Phys. 109, 2662 ~1998!#, as well as a significant number of new data for the HClO region of the surface at the same multirefe...

We examine the spatial temperature profile in the non-equilibrium relaxation region behind a stationary shock wave. The normal shock wave is established through a Mach reflection configuration from an opposing wedge arrangement for a hypervelocity air Mach 7.42 freestream. Schlieren images confirm that the shock configuration is steady and the location is repeatable. Emission spectroscopy is us...

A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron massvelocity and Darwin corrections. For H2 O, the PES has a dis...

Four different types of macroscopic models developed for the vibration-chemistry coupling in nonequilibrium flows for re-entry applications are presented. First, using an approach based on nonequilibrium thermodynamics, global rate coefficients of dissociation of N2 and O2 under parent molecular or atomic impact and backward molecular recombination are determined. Then a Two-Level Distribution ...

Analysis of the hot H2 16O spectrum, presented by Polyansky et al. (1996, J. Mol. Spectrosc. 176, 305-315), is extended to higher vibrational states. Three hundred thirty mainly strong lines are assigned to pure rotational transitions in the (100), (001), and (020) vibrational states. These lines, which involve significantly higher rotational energy levels than were known previously, are assign...

Photodetachment cross sections are measured across the detachment threshold of Au2(-) between 1.90 and 2.02 eV using a tunable laser. In addition to obtaining a more accurate electron affinity for Au2 (1.9393 ± 0.0003 eV), we observe eight resonances above the detachment threshold, corresponding to excitations from the vibrational levels of the Au2(-) ground state (X(2)Σu(+)) to those of a meta...

0301-0104/$ see front matter 2011 Elsevier B.V. A doi:10.1016/j.chemphys.2011.09.015 ⇑ Corresponding author. E-mail address: [email protected] (K.C. Janda). We present the first comprehensive ab initio study of the Ne–Br2 potential energy surfaces and the nonadiabatic couplings between the valence excited electronic states. These ab initio results are used to obtain 3-D approximate potentials for...

a theoretical study of the kinetic and mechanism of 3-aug-cope rearrangement in gas phase was performed usingdet methods at b3lyp levels of theory with 6-3114ig(d,p) bass set at 298.i5k. equilibrium moleculargeometries and harmonic vibrational frequencies of the reactant, transition state did product were calculated. then,rate constant and activation thermodynamics parameters were calculated an...