Decay Processes in Cationic Alkali Metals in Microsolvated Clusters: A Complex Absorbing Potential Based...

We have employed the highly accurate complex absorbing potential based ionization potential equation-of-motion coupled cluster singles and doubles (CAP-IP-EOM-CCSD) method to study the various intermolecular decay processes in ionized metals (Li⁺, Na⁺, K⁺) microsolvated by water molecules. For the Li atom, the electron is ionized from the 1s subshell. However, for Na and K atoms, the electron is ionized from 2s and both 2s and 2p subshells, respectively. We have investigated decay processes for the Li⁺-(H₂O) (n = 1-3) systems, as well as Na⁺-(H₂O) (n = 1, 2), and K⁺-H₂O. The lithium cation in water can decay only via electron transfer mediated decay (ETMD) as there are no valence electrons in lithium. We have investigated how the various decay processes change in the presence of different alkali metal atoms and how the increasing number of water molecules play a significant role in the decay of microsolvated systems. To see the effect of the environment, we have studied Li⁺-NH₃ in comparison to Li⁺-H₂O. In the case of Na⁺-H₂O, we have studied the impact of bond distance on the decay width. The effect of polarization on decay width was checked for the X⁺-H₂O (X = Li, Na) systems. We used the PCM model to study the polarization effect. We have compared our results with existing theoretical and experimental results wherever available in the literature.