TY - JOUR
T1 - Nonadiabatic behavior of a transition metal system
T2 - Exothermic reactions of Fe+(6D,4F) and propane
AU - Schultz, Richard H.
AU - Armentrout, P. B.
PY - 1987
Y1 - 1987
N2 - Guided ion beam mass spectrometry is used to investigate the exothermic reactions of Fe+ with propane, production of FeC2H4+ and FeC3H6+. By utilizing two well-characterized ion sources, we determine the reactivities of both the Fe+(6D) ground state and the Fe+(4F) first excited state. Above a kinetic energy of 0.4 eV, the latter is more reactive, consistent with previous results for the state-specific reactions of Fe+ + H2. Surprisingly, Fe+(6D) is the more reactive state below 0.4 eV. Since molecular orbital arguments suggest that the surfaces evolving from these states cross, the experimental observations are explained by adiabatic behavior at low energy and nonadiabatic (diabatic) behavior at high energies. Simple theoretical treatments such as Landau-Zener theory cannot account for the observed behavior.
AB - Guided ion beam mass spectrometry is used to investigate the exothermic reactions of Fe+ with propane, production of FeC2H4+ and FeC3H6+. By utilizing two well-characterized ion sources, we determine the reactivities of both the Fe+(6D) ground state and the Fe+(4F) first excited state. Above a kinetic energy of 0.4 eV, the latter is more reactive, consistent with previous results for the state-specific reactions of Fe+ + H2. Surprisingly, Fe+(6D) is the more reactive state below 0.4 eV. Since molecular orbital arguments suggest that the surfaces evolving from these states cross, the experimental observations are explained by adiabatic behavior at low energy and nonadiabatic (diabatic) behavior at high energies. Simple theoretical treatments such as Landau-Zener theory cannot account for the observed behavior.
UR - http://www.scopus.com/inward/record.url?scp=0343987034&partnerID=8YFLogxK
U2 - 10.1021/j100301a001
DO - 10.1021/j100301a001
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AN - SCOPUS:0343987034
SN - 0022-3654
VL - 91
SP - 4433
EP - 4435
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 17
ER -