Theoretical Appraisal of Cyclopropenone: Aggregation and Complexes with Water
Journal article, 2023

Cyclopropenone (HCCOCH, "CPN") is an exotic quasi-aromatic cyclic carbene that abounds in the interstellar medium (ISM). Astronomical observations suggest that (i) stagnate CPN exhibits a tendency to polymerize and that (ii) interactions may occur between CPN and water that is also ubiquitous in the ISM. In this light, density functional theory investigations reveal cooperative hydrogen bonding, which leads to stable polymeric conformations of (CPN)n, tracked up to n = 14. Stable agglomerations with water, however, constitute at best only two CPN and two water molecules, signifying that while CPN exhibits remarkable cooperativity for "cohesive" clustering via hydrogen bonding, this tendency is markedly diminished for "hetero"-interactions. Multifaceted data are employed to probe cogent molecular descriptors, such as structure and energetics of various conformers, vibrational spectroscopic response, molecular electrostatic potential (MESP), effective atomic charges: all these, in unison, describe the evolution of the characteristics upon cluster formation. Salient stretching frequency shifts, as well as charge redistribution gleaned from MESP morphology, have a direct bearing on variegated hydrogen bonding patterns: linear, nonlinear, as well as bifurcated. In particular, characteristic C-H, C═O stretching, and O-H vibrations in the water complexes reveal a "softening" (downshift) of frequencies. While small conformers have markedly distinct MESP variations, the differences become less pronounced with incremental clustering, an effect substantiated by corresponding emergent atomic charges.

Author

Vivekanand V. Gobre

Goa University

Soniya Rao

Chalmers, Physics, Materials Physics

Shridhar P. Gejji

Savitribai Phule Pune University

Libero J. Bartolotti

East Carolina University

Rajeev K. Pathak

Savitribai Phule Pune University

Journal of Physical Chemistry A

1089-5639 (ISSN) 1520-5215 (eISSN)

Vol. 127 29 6071-6080

Subject Categories

Chemical Process Engineering

Condensed Matter Physics

DOI

10.1021/acs.jpca.3c02937

PubMed

37463028

More information

Latest update

8/10/2023