On the dynamics of the selective electronic and vibrational excitation of nitrogen in the recombination between F− and N2+

Translational Energy Effects in the Excited Ca(1D2) + HCl → CaCl(A) + H Reaction. Experiments and a Harpooning Mechanism

“…Insight into the mechanism is obtained by treating nonadiabatic events at crossings independently, and combining them to give the total probability for each exit channel. The following discussion is along the lines of a recent treatment of a positive ion−negative ion recombination process . The probability P for production of CaCl can be given as a proper combination of p x , the probability of diabatic passage through the x th curve crossing ( x = 1, 2, 3 in Figure ).…”

“…In general (see, e.g., ref ) a crucial and elusive quantity to be assessed is the nonadiabatic coupling matrix element H x which we model as a decaying function of distance and specifically where α is assumed to be the same of the V 2 function introduced before on the ground that both V 2 and H x depend on the overlap between the asymptotic behavior of radical wave functions describing the electron orbitals before and after the electron jump. ,, We will see later that the preexponential factor A giving the absolute scale for H x is not (within a wide range of values) substantially affecting the energy dependence of cross sections but only their absolute values.…”

“…The following discussion is along the lines of a recent treatment of a positive ion-negative ion recombination process. 25 The probability P for production of CaCl can be given as a proper combination of p x , the probability of diabatic passage through the xth curve crossing (x ) 1, 2, 3 in Figure 4). For the calculation of p x we used the classic formula of Landau, Zener, and Stu ¨ckelberg: 26,27,28 where H x is the matrix element of nonadiabatic coupling at the xth crossing, ∆ x (Figure 4) is the absolute value of the difference between the slopes of the involved potential energy curves, and V R is the radial velocity at the same crossing given by µ is the reduced mass of the system, E is the collision energy in the center-of-mass frame, b is the impact parameter, E x and R x are energy and location of the xth crossing (Figure 4).…”

Stereoselectivity in Autoionization Reactions of Hydrogenated Molecules by Metastable Noble Gas Atoms: The Role of Electronic Couplings

“…Many other elementary chemical processes, such as ion‐recombination, energy transfer, and ion‐molecule reactions (see also refs. , and references therein) are triggered by an electron transfer.…”

“…In particular,t he chemiluminescent reaction mechanism hasb een found to be dependento nt he selective charge-transferh arpooning andc oncerted intermediate complex rearrangement. [15][16][17] Many other elementary chemical processes, such as ion-recombination, [18,19] energy transfer, [20] and ion-molecule reactions [21][22][23] (see also refs. [24], [ 25] and references therein)a re triggered by an electron transfer.T he selectivity in their dynamics is controlled by the criticalb alance of the kinetic energy with intermolecular interaction components, which include coupling terms by charge transferbetween entrance and exit channels.M oreover, excimer lasers, as those involving noble gas-halogen atom pairs, exhibit binding energies in allowed molecular states and transition moments between them strongly affected by the configurationi nteraction between neutral ground and ionic excited states of the same symmetry that differ for an electron exchange (see for instance ref.…”