Effect of protonation and deprotonation on electron transfer mediated decay and interatomic coulombic decay

TitleEffect of protonation and deprotonation on electron transfer mediated decay and interatomic coulombic decay
Publication TypeJournal Article
Year of Publication2023
AuthorsKumar, R, Vaval, N
JournalChemPhysChem
Volume24
Issue1
Date PublishedJAN
Type of ArticleArticle
ISSN1439-4235
Abstract

Electronically excited atoms or molecules in an environment are often subject to interatomic/intermolecular Coulombic decay (ICD) and/or electron transfer mediated decay (ETMD) mechanisms. A few of the numerous variables that can impact these non-radiative decay mechanisms include bond distance, the number of nearby atoms or molecules, and the polarisation effect. In this paper, we have studied the effect of protonation and deprotonation on the ionization potential (IP), double ionization potential (DIP), and lifetime (or decay width) of the temporary bound state in these non-radiative decay processes. We have chosen LiH-NH3 and LiH-H2O as test systems. The equation of motion coupled cluster singles and doubles method augmented by complex absorbing potential (CAP-EOM-CCSD) has been used in calculating the energetic position of the decaying state and the system's decay rate. Deprotonation of LiH-NH3/LiH-H2O either from the metal center (LiH) or from ammonia/water lowers the IP and DIP compared to the neutral systems. In contrast, protonation increases these quantities compared to neutral systems. The protonation closes the inner valence state relaxation channels for ICD/ETMD. For example, the decay of the O-2s/N-2s state stops in protonated systems (LiH2+-H2O, LiH2+-NH3, and LiH-NH4+). Our study also shows that the efficiency, i. e., the rate of ICD/ETMD, can be altered by protonation and deprotonation. It is expected to have implications for chemical and biological systems.

DOI10.1002/cphc.202200340
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

3.520

Divison category: 
Physical and Materials Chemistry
Database: 
Web of Science (WoS)

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