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4s to 5s and 4p photoexcitation dynamics of K atoms from the surface of helium nanodroplets: a theoretical study

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Abstract

We study the photodissociation of the potassium atom from a superfluid helium nanodroplet upon 5s 2S or 4p 2P excitation using the time-dependent helium density functional method (He-TDDFT). The importance of quantum effects is assessed by comparing the absorption spectrum obtained for a classical or a quantum description of the K atom. In the case of the 5s 2S ← 4s 2S excitation the difference is rather large, and we use a quantum description for the ensuing direct dissociation dynamics. In the case of the 4p 2P ← 4s 2S absorption spectrum, the difference is much smaller, hence a classical description of K is used to describe 4p 2P excitation dynamics. Excitation to the 4p 2Σ1/2 state leads to the direct dissociation of the K atom, while the 4p 2Π3/2 state initially leads to the formation of an exciplex and the 4p 2Π1/2 state to a bouncing atom above the droplet surface. Remarkably, electronic relaxation can be observed for the latter two states, leading to spin–orbit relaxation and the binding of the initially departing one-atom excimer as a ring excimer for the 2P3/2 state and to the formation of a bound, ring excimer for the 2Π1/2 state.

Graphical abstract: 4s to 5s and 4p photoexcitation dynamics of K atoms from the surface of helium nanodroplets: a theoretical study

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Publication details

The article was received on 17 Aug 2018, accepted on 10 Oct 2018 and first published on 11 Oct 2018


Article type: Paper
DOI: 10.1039/C8CP05253K
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
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    4s to 5s and 4p photoexcitation dynamics of K atoms from the surface of helium nanodroplets: a theoretical study

    M. Martinez, F. Coppens, M. Barranco, N. Halberstadt and M. Pi, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP05253K

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