Surface curvature effects in neutral and protonated water clusters: insights from DFT and energy decomposition analysis

Murillo H. Queiroz; Bruno S. Sampaio; Celine Nieuwland; Célia Fonseca Guerra; Tiago V. Alves; Roberto Rivelino

doi:10.1039/d6cp00702c

Surface curvature effects in neutral and protonated water clusters: insights from DFT and energy decomposition analysis

Murillo H. Queiroz
, Bruno S. Sampaio
, Celine Nieuwland
, Célia Fonseca Guerra
, Tiago V. Alves
, Roberto Rivelino^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

Polycyclic aromatic hydrocarbons (PAHs), abundant in interstellar cold dust grains, exhibit distinct interactions with neutral and cationic water clusters depending on carbon surface curvature. To investigate these effects, we have performed quantum-chemical calculations on the complexation of (H₂O)₅ (neutral water pentamer), H₃O⁺(H₂O)₃ (Eigen-type cation), and H₅O₂⁺(H₂O)₂ (Zundel-type cation) with planar coronene and curved corannulene. Our results reveal that the relative stability of neutral and cationic clusters is governed by both the number of O–H⋯π bonds and the concavity of the surface. For example, Eigen-type cation stabilizes in planar coronene and convex corannulene, while Zundel-type cation is slightly stabilized on concave corannulene. Infrared absorption features, including shifts and splittings of proton-transfer and O–H stretch modes, are assigned to these complexes, providing spectroscopic signatures of curvature-dependent interactions.

Original language	English
Pages (from-to)	12623-12631
Number of pages	9
Journal	Physical Chemistry Chemical Physics
Volume	28
Issue number	20
Early online date	16 Apr 2026
DOIs	https://doi.org/10.1039/d6cp00702c
Publication status	Published - 27 May 2026

Bibliographical note

Publisher Copyright:
This journal is © the Owner Societies, 2026.

Funding

This work was partially supported by Brazilian funding agencies: Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Finance Code 001), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), and Fundação de Amparo à Pesquisa do Estado da Bahia (FAPESB). MHQ acknowledges CAPES-Brazil for the internship scholarship, and RR acknowledges support from CNPq (Grant No. 309356/2025-3). The authors also thank the National Laboratory for Scientific Computing (LNCC/MCTI, Brazil) for providing HPC resources through the SDumont supercomputer. CN and CFG acknowledge financial support from the Dutch Research Council (NWO). This work was also partially carried out on the Dutch national e-infrastructure with the support of SURF Cooperative and the ADA HPC facility of Vrije Universiteit Amsterdam.

Funders	Funder number
National Laboratory for Scientific Computing
LNCC
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
SURF
Fundação de Amparo à Pesquisa do Estado da Bahia
Conselho Nacional de Desenvolvimento Científico e Tecnológico
Ministério da Ciência, Tecnologia e Inovação
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior	309356/2025-3

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title = "Surface curvature effects in neutral and protonated water clusters: insights from DFT and energy decomposition analysis",

abstract = "Polycyclic aromatic hydrocarbons (PAHs), abundant in interstellar cold dust grains, exhibit distinct interactions with neutral and cationic water clusters depending on carbon surface curvature. To investigate these effects, we have performed quantum-chemical calculations on the complexation of (H2O)5 (neutral water pentamer), H3O+(H2O)3 (Eigen-type cation), and H5O2+(H2O)2 (Zundel-type cation) with planar coronene and curved corannulene. Our results reveal that the relative stability of neutral and cationic clusters is governed by both the number of O–H⋯π bonds and the concavity of the surface. For example, Eigen-type cation stabilizes in planar coronene and convex corannulene, while Zundel-type cation is slightly stabilized on concave corannulene. Infrared absorption features, including shifts and splittings of proton-transfer and O–H stretch modes, are assigned to these complexes, providing spectroscopic signatures of curvature-dependent interactions.",

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AU - Queiroz, Murillo H.

AU - Sampaio, Bruno S.

AU - Nieuwland, Celine

AU - Guerra, Célia Fonseca

AU - Alves, Tiago V.

AU - Rivelino, Roberto

PY - 2026/5/27

Y1 - 2026/5/27

N2 - Polycyclic aromatic hydrocarbons (PAHs), abundant in interstellar cold dust grains, exhibit distinct interactions with neutral and cationic water clusters depending on carbon surface curvature. To investigate these effects, we have performed quantum-chemical calculations on the complexation of (H2O)5 (neutral water pentamer), H3O+(H2O)3 (Eigen-type cation), and H5O2+(H2O)2 (Zundel-type cation) with planar coronene and curved corannulene. Our results reveal that the relative stability of neutral and cationic clusters is governed by both the number of O–H⋯π bonds and the concavity of the surface. For example, Eigen-type cation stabilizes in planar coronene and convex corannulene, while Zundel-type cation is slightly stabilized on concave corannulene. Infrared absorption features, including shifts and splittings of proton-transfer and O–H stretch modes, are assigned to these complexes, providing spectroscopic signatures of curvature-dependent interactions.

AB - Polycyclic aromatic hydrocarbons (PAHs), abundant in interstellar cold dust grains, exhibit distinct interactions with neutral and cationic water clusters depending on carbon surface curvature. To investigate these effects, we have performed quantum-chemical calculations on the complexation of (H2O)5 (neutral water pentamer), H3O+(H2O)3 (Eigen-type cation), and H5O2+(H2O)2 (Zundel-type cation) with planar coronene and curved corannulene. Our results reveal that the relative stability of neutral and cationic clusters is governed by both the number of O–H⋯π bonds and the concavity of the surface. For example, Eigen-type cation stabilizes in planar coronene and convex corannulene, while Zundel-type cation is slightly stabilized on concave corannulene. Infrared absorption features, including shifts and splittings of proton-transfer and O–H stretch modes, are assigned to these complexes, providing spectroscopic signatures of curvature-dependent interactions.

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Surface curvature effects in neutral and protonated water clusters: insights from DFT and energy decomposition analysis

Abstract

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