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A Path Integral Molecular Dynamics Simulation of a Harpoon-Type Redox Reaction in a Helium Nanodroplet
- Source :
- Molecules, Molecules, Vol 26, Iss 5783, p 5783 (2021), Digital.CSIC. Repositorio Institucional del CSIC, instname, Volume 26, Issue 19
- Publication Year :
- 2021
- Publisher :
- MDPI, 2021.
-
Abstract
- 20 pags., 12 figs., 2 tabs. -- This article belongs to the Special Issue Reactivity and Properties of Radicals and Radical Ions<br />We present path integral molecular dynamics (PIMD) calculations of an electron transfer from a heliophobic Cs dimer in its () state, located on the surface of a He droplet, to a heliophilic, fully immersed C molecule. Supported by electron ionization mass spectroscopy measurements (Renzler et al., J. Chem. Phys.2016, 145, 181101), this spatially quenched reaction was characterized as a harpoon-type or long-range electron transfer in a previous high-level ab initio study (de Lara-Castells et al., J. Phys. Chem. Lett.2017, 8, 4284). To go beyond the static approach, classical and quantum PIMD simulations are performed at 2 K, slightly below the critical temperature for helium superfluidity (2.172 K). Calculations are executed in the NVT ensemble as well as the NVE ensemble to provide insights into real-time dynamics. A droplet size of 2090 atoms is assumed to study the impact of spatial hindrance on reactivity. By changing the number of beads in the PIMD simulations, the impact of quantization can be studied in greater detail and without an implicit assumption of superfluidity. We find that the reaction probability increases with higher levels of quantization. Our findings confirm earlier, static predictions of a rotational motion of the Cs dimer upon reacting with the fullerene, involving a substantial displacement of helium. However, it also raises the new question of whether the interacting species are driven out-of-equilibrium after impurity uptake, since reactivity is strongly quenched if a full thermal equilibration is assumed. More generally, our work points towards a novel mechanism for long-range electron transfer through an interplay between nuclear quantum delocalization within the confining medium and delocalized electronic dispersion forces acting on the two reactants.<br />This work has been partly supported by the Spanish Agencia Estatal de Investigación (AEI) and the Fondo Europeo de Desarrollo Regional (FEDER, UE) under Grant Nos. PID2020-114654GB I00, PID2020-117605GB-I00, FIS2017-83157-P, MAT2016-75354-P and by the Austrian Science Fund (FWF) under Grant P29893-N36
- Subjects :
- path integral molecular dynamics simulations
redox reaction
harpoon mechanism
charge transfer process
Pharmaceutical Science
Helium nanodroplets
Organic chemistry
London dispersion force
Article
Analytical Chemistry
Superfluidity
Delocalized electron
Quantization (physics)
Electron transfer
QD241-441
Ab initio quantum chemistry methods
Charge transfer process
Drug Discovery
Path integral molecular dynamics
Physics::Atomic and Molecular Clusters
Redox reaction
Physical and Theoretical Chemistry
Electron ionization
Non-adiabatic couplings
Physics
Harpoon mechanism
ab initio calculations
superfluid helium
non-adiabatic couplings
Chemistry (miscellaneous)
Chemical physics
helium nanodroplets
Path integral molecular dynamics simulations
Molecular Medicine
Ab initio calculations
Superfluid helium
Subjects
Details
- Language :
- English
- ISSN :
- 14203049
- Volume :
- 26
- Issue :
- 19
- Database :
- OpenAIRE
- Journal :
- Molecules
- Accession number :
- edsair.doi.dedup.....c14bc8084a6d87dc322715949a943c81