Deciphering the Impact of Helium Tagging on Flexible Molecules: Probing Microsolvation Effects of Protonated Acetylene by Quantum Configurational Entropy

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 127; no. 11; pp. 2460 - 2471
• Main Authors: Beckmann, Richard, Topolnicki, Rafal, Marx, Dominik
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 23.03.2023
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• DOI: 10.1021/acs.jpca.2c08967
• ISSN: 1089-5639; 1520-5215

Helium, the lightest and most weakly interacting noble gas, is well-known for its unsurpassed chemical inertness. In many applications of helium in experimental techniques, such as tagging, messenger, or nanodroplet isolation action spectroscopy of molecules or complexes, it is assumed that the interaction of helium with the respective species, and thus the resulting interaction-induced perturbation, is small enough not to affect their structure and dynamics. Here, we probe the impact of one up to many attached helium atoms on protonated acetylenean important nonclassical carbocation subject to three-center two-electron bonding in its ground state structureusing highly accurate interaction potentials in conjunction with entropy-based higher-order nonlinear correlation analysis. In particular, using neural network potentials at CCSD­(T) accuracy, we disclose the specific structural perturbations due to the tagging of C2H3 + with up to 20 He atoms at a temperature of 1 K. Analysis reveals that microsolvation by helium influences the structure of C2H3 + noticeably, while our investigation of the quantum configurational information entropy additionally shows that correlations between individual orientational degrees of freedom are affected as a function of cluster size. In particular, it is found that the most probable bridge-like structure of the ro-vibrational quantum ground state of C2H3 +, which is nonplanar and trans-bent in contrast to the perfectly planar equilibrium structure, becomes increasingly more localized upon adding helium atoms. The remarkably nonlinear behavior of the angular correlations as a function of cluster size is traced back to the buildup of the quantum microsolvation shell that enhances anisotropy up to N He = 6 while more and more isotropic solvation takes over beyond six. Our approach is general and thus sets the stage to investigate the salient effects on the structure of flexible molecules due to tagging beyond the specific case.