A realistic hydroperoxo(~X2A") potential energy surface from the double many-body expansion method

Abstract

nuclei interacting with Ln3+ ions (in which case y in eq 3 refers to the nucleus and r to the electron-nuclear distance). As part of an NMR study of lanthanidebound micelles, we have measured the proton Ti relaxation times for SDS micelles (0.07 M surfactant) to which a variety of Ln3+ ions (0.002 M) had been added.22 The quantity of interest, plotted as hollow squares in Figure 1, is the relaxation enhancement for the CH, group in SDS bound directly to the sulfate, defined of dipolar Ti enhancements (hollow squares) does not match the pattern of k, values (filled squares). This argues against a significant dipolar contribution to k,. ConclusionWe have measured bimolecular quenching rate constants k, for interaction of lanthanide ions with the 1,9-biradical 2. The evidence so far suggests that spin exchange is the principal quenching mechanism. The dipolar mechanism does not appear to have a major influence on the quenching. Further investigations, including the magnetic field dependence and chain length dependence of k,, and lanthanide effect on intramolecular product ratios, are in progress. A double many-body expansion potential energy surface reported previously for H02(R2A") and referred to here as DMBE I is modified to produce thermal rate coefficients for the reaction 0 + OH -O2 + H in good agreement with experiment. Acknowledgment. The authors thank theThis new potential energy surface will be referred to as DMBE 11. By the further imposition that the potential function should reproduce the experimental spectroscopic force field data for the hydroperoxyl radical, another potential energy surface has been obtained, DMBE 111. Both of these improved DMBE I1 and DMBE 111 potential energy surfaces preserve the functional form used previously for DMBE I except for the long-range 0. -.OH electrostatic interaction, which is defined in the spirit of a more satisfactory adiabatic theory.

A Quasiclassical Trajectory Study of the Reaction of H Atoms with O2(1Δg)

“…Due to its importance, the reaction has been the subject of a large number of studies, both experimental and theoretical. 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27 A large body of information is available on the reaction of H atoms with oxygen molecules in the electronic ground state,…”

Dynamics of Complex-Forming Bimolecular Reactions: A Comparative Theoretical Study of the Reactions of H Atoms with O2(3Σg–) and O2(1Δg)

“…5,6 . In addition to extensive reaction kinetics work 7,8,9,10,11,12,13,14,15, , numerous theoretical studies , 16,17,18,19,20,21,22,23,24,25,26,27,28,29,30 have been performed to describe the dynamics of the reaction of ground-state molecular oxygen,…”

Quantum control of isomerization by robust navigation in the energy spectrum

“…The Li-CN molecule is a triatomic floppy molecule, 48,49 within a class which includes, for example, H-CN, 50 Na-CN, 48 K-CN, 48,51 H 3 C-CN, 52 H-CP, 53 and the H-O 2 radical, 54 or the van der Waals complexes, 55 such as He-FH, He-ClH, He-BrH, and He-CNH.…”