Ab initio molecular dynamics study of solvated electrons in methanol clusters

Abstract

Stable surface excess electronic states in small methanol cluster anions were identified and characterized in ab initio molecular dynamics simulations.

Excess electron solvation in ammonia clusters

“…This is consistent with the picture that neutral methanol clusters are covered on the surface mainly by the apolar methyl groups. 36,40 The excess electron in all examined cases localized mainly outside the cluster, in a very diffuse state with predominant surface character. Initial localization in the interior of the ammonia clusters is not observed.…”

“…We have recently employed BHandHLYP successfully in AIMD simulations of methanol cluster anions. 36 In a preceding benchmarking study we pointed out that due to its Hartee-Fock exchange component the BHandHLYP/6-31(1+3+)G(d) method provides a reasonable estimate of the VDE in small methanol cluster anions (n = 2 -8), and the BHandHLYP computed VDE values strongly correlate with those of MP2 using the same basis set. 40 Here, the argument based on the comparison with MP2/6-31(1+3+)G(d) VDE values is sensibly justified by a previously developed strong correlation between the VDE values at MP2/6-31(1+3+)G(d) and eom-EA-CCSD/aug3-cc-pVDZ levels for small water cluster anions.…”

“…These functionals have been employed in several ab initio molecular dynamics studies of aqueous and non-aqueous solvated electrons. 32,33,34,35,36 This fact motivated our choice. Of the employed theoretical methods, while B3LYP and PBE0 have been demonstrated to overestimate excess electron binding, 37 the BHandHLYP functional predicted acceptable agreement with MP2 numbers.…”

“…We reached similar conclusions in our quantum chemical and AIMD studies of negatively charged methanol clusters. 36,40 The most stable linear configurations contain only single hydrogen-bond acceptor/single donor molecules within the chains. Such structures are illustrated in Figures 2 and 3 with their representative spin density isosurfaces.…”

The influence of the FeCp(CO)2+moiety on the dynamics of the metalloid [Ge9(Si(SiMe3)3)3]−cluster in thf: synthesis and characterization by time-resolved absorption spectroscopy

“…Such studies would open a new way to contribute to elucidating mechanistic steps of the long-lasting issue of how electron detachment and localization in polar liquids can be quantitatively understood. [41][42][43][44][45] Experimental…”