Symmetry-induced kinetic isotope effects in the dissociation dynamics of CHCl₃+ and CHCl₄−

TY - JOUR

T1 - Symmetry-induced kinetic isotope effects in the dissociation dynamics of CHCl3+ and CHCl4−

AU - Petersen, Allan Christian

AU - Sølling, Theis I.

AU - Waters, Max D.j.

PY - 2018/11/14

Y1 - 2018/11/14

N2 - Loss of Cl from CHCl3 + with little excess energy is found to proceed via two distinct pathways, the reaction channel which is being followed is determined by a symmetry-induced kinetic isotope effect. Computational investigations suggest competition between a statistical adiabatic process and a process of electronic predissociation. For CHCl4 − and CH2Cl3 −, rotational predissociation contributes to the kinetic isotope effects for all isotopomers, whereas the particularly large effect observed for CH35Cl3 37Cl− also originates from symmetry-induced degeneracy of vibrational modes in the C3V point.

AB - Loss of Cl from CHCl3 + with little excess energy is found to proceed via two distinct pathways, the reaction channel which is being followed is determined by a symmetry-induced kinetic isotope effect. Computational investigations suggest competition between a statistical adiabatic process and a process of electronic predissociation. For CHCl4 − and CH2Cl3 −, rotational predissociation contributes to the kinetic isotope effects for all isotopomers, whereas the particularly large effect observed for CH35Cl3 37Cl− also originates from symmetry-induced degeneracy of vibrational modes in the C3V point.

U2 - 10.1016/j.chemphys.2018.07.051

DO - 10.1016/j.chemphys.2018.07.051

M3 - Journal article

SN - 0301-0104

VL - 515

SP - 375

EP - 380

JO - Chemical Physics

JF - Chemical Physics

ER -