Outer Valence Intermolecular Coulombic Decay in Hydrogen-Bonded Complexes Induced by Resonant Two-Photon Excitation by 4.4 eV Photons

Photoexcitation of van der Waals complexes can lead to several decay pathways depending on the nature of the potential energy surfaces. Upon excitation of a chromophore in a complex, ionization of its weakly bound neighbour via energy transfer happens via a unique relaxation process known as intermo...

Full description

Saved in:
Bibliographic Details
Published in:arXiv.org 2022-01
Main Authors: Bejoy, Namitha Brijit, Singh, Nitin K, Pananghat, Balanarayan, Patwari, G Naresh
Format: Article
Language:English
Subjects:
Aliphatic amines
Chromophores
Decay
Electronic structure
Energy transfer
Hydrogen bonding
Imaging techniques
Kinetic energy distribution
Near ultraviolet radiation
Photoexcitation
Photons
Potential energy
Trimethylamine
Ultraviolet radiation
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Photoexcitation of van der Waals complexes can lead to several decay pathways depending on the nature of the potential energy surfaces. Upon excitation of a chromophore in a complex, ionization of its weakly bound neighbour via energy transfer happens via a unique relaxation process known as intermolecular Coulombic decay (ICD); a phenomenon of renewed focus owing to its relevance in biological systems. Herein, we report an experimental evidence of outer-valence ICD induced by multiphoton excitation by near UV radiation of 4.4 eV photons, hitherto unknown in molecular systems. In the binary complexes of 2,6-difluorophenylacetylene with aliphatic amines such as dimethylamine and trimethylamine a resonant two-photon excitation is localized on the 2,6-difluorophenylacetylene chromophore. The absorbed energy is then transferred to its hydrogen-bonded partner amine and resulting in the formation of an amine cation. The kinetic energy distribution of the amine cations is invariant with respect to the initial geometry of the binary complex. The present experimental results combined with electronic structure calculations provide valuable insights into the nature of ICD in van der Waals complexes and more importantly, the role of ICD as a fast, efficient, and prominent decay channel following excitation at modest (4.4 eV) photon energies.
ISSN:2331-8422