Excess electron solvation in ammonia clusters

Baranyi, Bence and Turi, László (2019) Excess electron solvation in ammonia clusters. JOURNAL OF CHEMICAL PHYSICS, 151 (20). p. 204304. ISSN 0021-9606

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Abstract

We performed a combination of quantum chemical calculations and molecular dynamics simulations to assess the stability of various size ("N" "H" _"3" )_n^- ammonia cluster anions up to n = 32 monomers. In the n = 3 – 8 size range, cluster anions are optimized and the vertical detachment energy of the excess electron (VDE) from increasing size clusters are computed using various level methods including density functional theory (DFT), MP2 and CCSD(T) calculations. These clusters bind the electron in non-branched hydrogen bonding chains in dipole bound states. The VDE increases with size from a few meV up to ~200 meV. The electron binding energy is weaker than in water clusters but comparable to small methanol cluster VDEs. We located the first branched hydrogen bonding cluster that binds the excess electron at n = 7. For larger (n = 8 – 32) clusters we generated cold, neutral clusters by semiempirical and ab initio molecular dynamics (AIMD) simulations, and added an extra electron to selected neutral configurations. VDE calculations on the adiabatic and the relaxed anionic structures suggest that the n = 12 - 32 neutral clusters weakly bind the excess electron. Electron binding energies for these clusters (~ 100 meV) appear to be significantly weaker than extrapolated from experimental data. The observed excess electron states are diffuse and localized outside the molecular frame (surface states) with minor (~1%) penetration to the nitrogen frontier orbitals. Stable minima with excess electron states surrounded by solvent molecules (cavity states) were not found in this size regime.

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