Excess electrons in methanol clusters: Beyond the one-electron picture

Pohl, Gábor; Mones, Letif; Túri, László

doi:10.1063/1.4964845

Cited by 6 publications

(26 citation statements)

References 71 publications

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“…35,48 In these studies, one-electron simulations were used to generate cluster configurations of different size 35 that, in turn, were analyzed in many-electron computations. 48 In the QCMD part, we produced two 100 ps long equilibrium trajectories of canonical ensembles at 200 K, one for (CH 3 OH) clusters with interior state excess electrons, and one for (CH 3 OH) clusters with surface-bound excess electrons. 35 Here, we select ten configurations from each of these equilibrium trajectories, evenly separated by 10 ps time segments.…”

Section: Methodsmentioning

confidence: 99%

“…The small clusters are generated similarly to those in our previous studies. 47,48 We determine the center of mass of the solvated electron using the one-electron pseudopotential, and cut out clusters of gradually increasing size consisting of n methanol molecules (n = 8, 16, and 32) that are nearest to the center of mass of the electron. These clusters are thought to model the first, the second and (partly) the third solvation shells of the excess electron.…”

Section: Methodsmentioning

confidence: 99%

“…47 In surface state configurations the dipole moment of the cluster and possibly dangling OH hydrogens localize the excess electron. 48 In the present work we use DFT for the electronic structure calculations with the BHandHLYP functional. 50,51 We have recently shown 48 .…”

Section: Methodsmentioning

confidence: 99%

“…48 In the present work we use DFT for the electronic structure calculations with the BHandHLYP functional. 50,51 We have recently shown 48 . We also demonstrated that the BHandHLYP VDE values strongly correlate with those of MP2 using the same basis set.…”

Section: Methodsmentioning

confidence: 99%

“…45,46 Correlated ab initio calculations on water and methanol cluster anions, however, demonstrated that proper benchmarking of the applied functionals and basis sets is of essential importance if one aims to go beyond the semi-quantitative interpretation of the experimental data. 47,48 We found that while neither the PBE, nor the BLYP functionals reproduce the VDE of water and methanol cluster anions with sufficient accuracy, the long range corrected BLYP (LC-BLYP) 45,46,49 and the hybrid BHandHLYP functional 50,51 provide a much better estimate. The available hardware also places a limit on the size of the investigated system and the length of the trajectories.…”

Section: Introductionmentioning

confidence: 98%

See 4 more Smart Citations

Ab initio molecular dynamics study of solvated electrons in methanol clusters

Mones

Pohl

Túri

2018

Phys. Chem. Chem. Phys.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

See 3 more Smart Citations

Ab initio molecular dynamics study of solvated electrons in methanol clusters

Mones

Pohl

Túri

2018

Phys. Chem. Chem. Phys.

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Coordination of anions by noncovalently bonded σ-hole ligands

Scheiner

Michalczyk

Zierkiewicz

2020

Coordination Chemistry Reviews

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Ab Initio Molecular Dynamics Simulations of Solvated Electrons in Ammonia Clusters

Baranyi

Túri

2020

J. Phys. Chem. B

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We investigated excess electron solvation dynamics in (NH 3 ) n – ammonia clusters in the n = 8–32 size range by performing finite temperature molecular dynamics simulations. In particular, we focused on three possible scenarios. The first case is designed to model electron attachment to small neutral ammonia clusters ( n ≤ ∼10) that form hydrogen-bonded chains. The excess electron is bound to the clusters via dipole bound states, and persists with a VDE of ∼160 meV at 100 K for the n = 8 cluster. The coupled nuclear and electronic relaxation is fast (within ∼100 fs) and takes place predominantly by intermolecular librational motions and the intramolecular umbrella mode. The second scenario illustrates the mechanism of excess electron attachment to cold compact neutral clusters of medium size (8 ≤ n ≤ 32). The neutral clusters show increasing tendency with size to bind the excess electron on the surface of the clusters in weakly bound, diffuse, and highly delocalized states. Anionic relaxation trajectories launched from these initial states provide no indication for excess electron stabilization for sizes n < 24. Excess electrons are likely to autodetach from these clusters. The two largest investigated clusters ( n = 24 and 32) can accommodate the excess electron in electronic states that are mainly localized on the surface, but they may be partly embedded in the cluster. In the last 500 fs of the simulated trajectories, the VDE of the solvated electron fluctuates around ∼200 meV for n = 24 and ∼500 meV for n = 32, consistent with the values extrapolated from the experimentally observed linear VDE– n –1/3 trend. In the third case, we prepared neutral ammonia cluster configurations, including an n = 48 cluster, that contain possible electron localization sites within the interior of the cluster. Excess electrons added to these clusters localize in cavities with high VDEs up to 1.9 eV for n = 48. The computed VDE values for larger clusters are considerably higher than the experimentally observed photoelectric threshold energy for the solvated electron in bulk ammonia (∼1.4 eV). Molecular dynamics simulations launched from these initial cavity states strongly indicate, however, that these cavity structures exist only for ∼200 fs. During the relaxation the electron leaves the cavity and becomes delocalized, while the cluster loses its initial compactness.

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Excess electrons in methanol clusters: Beyond the one-electron picture

Cited by 6 publications

References 71 publications

Ab initio molecular dynamics study of solvated electrons in methanol clusters

Ab initio molecular dynamics study of solvated electrons in methanol clusters

Coordination of anions by noncovalently bonded σ-hole ligands

Ab Initio Molecular Dynamics Simulations of Solvated Electrons in Ammonia Clusters

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