Work

Molecular Association and Reactivity of the Pyridine Dimer Cation

Year: 2024

Type: article

Abstract: , 12, 4936-4943]. Herein, the dynamics and consequent reactivity of the pyridine dimer cation were investigated employing Born-Oppenheimer molecular dynamics (BOMD) simulations. An antiparallel π-stacked pyridine dimer in the neutral ground state is transformed into a noncovalently interacting C-H···N hydrogen-bonded structure which can lead to proton transfer in the cationic state. Additionally, C-N- and N-N-bonded adducts were formed in the cationic state. Further, metastable C-H···H-C-bonded cationic species was observed, which rearranged to an N-N bonded adduct. In contrast to the experimental observation, migration of the proton to the α position was not observed in the C-N bonded adduct owing to a high barrier of about 2 eV. The observed trends in the molecular association, proton transfer, and the formation of C-N and N-N bonded adducts are a consequence of the roaming dynamics of one pyridine moiety over the other in the cationic state.

Source: The Journal of Physical Chemistry A

DOI: 10.1021/acs.jpca.4c04912

Authors: Amol Tagad, G. Naresh Patwari

Institution: Indian Institute of Technology Bombay

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green

Funders: Indian Institute of Technology Bombay, Indian Institute of Technology Guwahati, Science and Engineering Research Board, Board of Research in Nuclear Sciences

Awards: G4342951883, G6295783718