Fragmentation of ionized doped helium nanodroplets: Theoretical evidence for a dopant ejection mechanism

被引:51
作者
Bonhommeau, D. [1 ]
Lewerenz, M. [2 ]
Halberstadt, N. [3 ,4 ]
机构
[1] Univ Minnesota, Minneapolis, MN 55455 USA
[2] Univ Paris 06, UMR 7075, Lab Dynam Interact & React, CNRS, F-75252 Paris, France
[3] Univ Toulouse 3, Lab Collis Agregates React, IRSAMC, F-31062 Toulouse 09, France
[4] CNRS, Lab Collis Agregates React, IRSAMC, F-31062 Toulouse 09, France
关键词
D O I
10.1063/1.2823101
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We report a theoretical study of the effect induced by a helium nanodroplet environment on the fragmentation dynamics of a dopant. The dopant is an ionized neon cluster Ne-n(+) (n=4-6) surrounded by a helium nanodroplet composed of 100 atoms. A newly designed mixed quantum/classical approach is used to take into account both the large helium cluster zero-point energy due to the light mass of the helium atoms and all the nonadiabatic couplings between the Ne-n(+) potential-energy surfaces. The results reveal that the intermediate ionic dopant can be ejected from the droplet, possibly with some helium atoms still attached, thereby reducing the cooling power of the droplet. Energy relaxation by helium atom evaporation and dissociation, the other mechanism which has been used in most interpretations of doped helium cluster dynamics, also exhibits new features. The kinetic energy distribution of the neutral monomer fragments can be fitted to the sum of two Boltzmann distributions, one with a low kinetic energy and the other with a higher kinetic energy. This indicates that cooling by helium atom evaporation is more efficient than was believed so far, as suggested by recent experiments. The results also reveal the predominance of Ne-2(+) and HeqNe2+ fragments and the absence of bare Ne+ fragments, in agreement with available experimental data (obtained for larger helium nanodroplets). Moreover, the abundance in fragments with a trimeric neon core is found to increase with the increase in dopant size. Most of the fragmentation is achieved within 10 ps and the only subsequent dynamical process is the relaxation of hot intermediate HeqNe2+ species to Ne-2(+) by helium atom evaporation. The dependence of the ionic fragment distribution on the parent ion electronic state reached by ionization is also investigated. It reveals that HeqNe+ fragments are produced only from the highest electronic state, whereas HeqNe2+ fragments originate from all the electronic states. Surprisingly, the highest electronic states also lead to fragments that still contain the original ionic dopant species. A mechanism is conjectured to explain this fragmentation inhibition. (c) 2008 American Institute of Physics.
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页数:17
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