Infrared Spectroscopy of HOCl in the 4000-10 000 cm−1 Region

Ab Initio Studies of ClOx Reactions: VI. Theoretical Prediction of Total Rate Constant and Product Branching Probabilities for the HO2 + ClO Reaction

“…Tables and list the calculated geometry parameters, moments of inertia, and frequencies of the reactants and products, as well as the available experimental values for them. From Table , it can be seen that the bond lengths and bond angles in these species optimized at the B3LYP/6-311+G(3df,2p) level are close to the experimental values − except those of ClOO. The differences in the bond length and bond angle of ClOO between the predicted and the experimental values reach 0.420 Å and 6.3°, respectively.…”

Quantum Calculation of Ro-vibrational States: Methodology and DOCl Application Results

“…The third column contains the results calculated with the present quantum Lanczos method on the new PES, whereas the fourth column contains the results from previous Lanczos subspace filter diagonalization method on the old ab initio PES . The fifth column provides the reported results from Bowman et al, and the last column gives the available spectroscopic data. ,− Inspection of the table indicates that the new version of the pure ab initio PES generates the vibrational energies, which are in much better agreement with the available experimental data and with the early results of Bowman et al It is important to stress again at this point that the PES of Nanbu et al that we use in this paper is a genuine ab initio surface, without being scaled and/or inverted to reproduce the 22 available experimental vibrational bound state energies, as was previously done for the other two high-quality ab initio PESs. , Another technical point is that spline interpolation of potential energies at grid points has been applied in this PES, whereas in the other two PESs, fitted analytical expansions have been used. The new global ab initio PES gives a better representation about the minimum, because it has been developed and tested initially with a view to reactive scattering calculations.…”

“…41 The fifth column provides the reported results from Bowman et al, 34 and the last column gives the available spectroscopic data. 30,[52][53][54][55] Inspection of the table indicates that the new version of the pure ab initio PES generates the vibrational energies, which are in much better agreement with the available experimental data and with the early results of Bowman et al It is important to stress again at this point that the PES of Nanbu et al 40 that we use in this paper is a genuine ab initio surface, without being scaled and/or inverted to reproduce the 22 available experimental vibrational bound state energies, as was previously done for the other two high-quality ab initio PESs. 38,39 Another technical point is that spline interpolation of potential energies at grid points has been applied in this PES, whereas in the other two PESs, fitted analytical expansions have been used.…”

HOCl Ro-Vibrational Bound-State Calculations for Nonzero Total Angular Momentum

“…In this table, the second column contains the spectroscopic assignments of the states with ν 1 , ν 2 , and ν 3 being the number of quanta in the OH stretching, HOCl bending, and OCl stretching local modes, respectively. The third column contains the results calculated with the present quantum LHFD method, while the fourth column provides the reported results from Bowman et al The last column gives the available spectroscopic data. ,− Inspection of the energies shows that they are in general agreement, but because of different PESs and/or different methods employed, the differences for some bound states are still relatively large. It is important to stress again at this point that the PES of Nanbu et al.…”