2-in-1 Phase Space Sampling for Calculating the Absorption Spectrum of the Hydrated Electron.

The investigation of vibrational effects on absorption spectrum calculations often employs Wigner sampling or thermal sampling. While Wigner sampling incorporates zero-point energy, it may not be suitable for flexible systems. Thermal sampling is applicable to anharmonic systems yet treats nuclei classically.

Ab Initio Molecular Dynamics Simulations of Solvated Electrons in Ammonia Clusters.

We investigated excess electron solvation dynamics in (NH) ammonia clusters in the = 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 ( ≤ ∼10) that form hydrogen-bonded chains.

Excess electron solvation in ammonia clusters.

We performed a combination of quantum chemical calculations and molecular dynamics simulations to assess the stability of various size NH 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 is computed using various level methods including density functional theory, MP2, and coupled-cluster singles doubles with perturbative triples. These clusters bind the electrons in nonbranched hydrogen bonding chains in dipole bound states.