A new possibility of chemical bonding: vibrational stabilization of IHI

Exact quantum and vibrationally adiabatic quantum, semiclassical and quasiclassical study of the collinear reactions Cl + MuCl, Cl + HCl, Cl + DCl

“…This corresponds to a new kind of bound state that exists on a minimum free potential energy surface. It has been analysed in detail in [74,[78][79][80] as well in three dimensional calculations [80][81][82]. At higher energies these bound states become resonances of the kind discussed above for C1HCI and CIDCI.…”

Local and hyperspherical mode approximations to resonances in collinear atom–diatom reactions

“…In contrast, smaller MB/MA implies a smaller skewing angle cJ>M, and the prediction of resonances by the DIV AH and VIV AH methods becomes even more accurate (see Refs. [38][39][40][41][42]. The first application of the stabilization method for the calculation of resonances in reactive scattering was by Thompson and Truhlar.…”

First-principles simulations of transition state spectra of the I + HI and I + DI reactions and vibrational bonding in IMuI

“…This naturally leads to slow energy transfer between these two vibrational motions and then to relatively sharp resonance phenomena in reactive scattering, where the resonance wavefunctions are nearly localized around transition state regions of the potential energy surfaces. These theoretical studies have also showed the possible existence of ''vibrational-bonding'' phenomena [1][2][3][4][5][6][7], where such a ''transition state resonance'' becomes a true bound state if the light atom transfer barrier is sufficiently low and the resonance energy level is lower than the asymptotic zero-point energy levels of the HL and H 0 L diatomic molecules. Motivated by these early theoretical findings, Neumark and coworkers carried out so-called transition state spectroscopy experiments to observe resonance phenomena in chemical reactions using a sophisticated photodetachment technique [17][18][19][20][21][22][23][24][25][26][27].…”

“…HL + H 0 , which involve the transfer of a light atom L from one heavy atom H 0 to a second heavy atom H were extensively studied in the 1980s from the theoretical side [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Due to the large differences in the masses of the light and heavy atoms, the reaction systems have very different time scales between symmetric (H À H 0 stretch) and anti-symmetric (light atom motion corresponding to the reaction coordinate motion) vibrational motions at the transition-state.…”