Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains

Cahlík, Aleš; Hellerstedt, Jack; Mendieta‐Moreno, Jesús I.; Švec, Martin; Santhini, Vijai M.; Pascal, Simon; Soler-Polo, Diego; Erlingsson, Sigurdur I.; Výborný, Karel; Mutombo, Pingo; Maršálek, Ondřej; Siri, Olivier; Jelı́nek, Pavel

doi:10.1021/acsnano.1c02572

Cited by 14 publications

(19 citation statements)

References 51 publications

(87 reference statements)

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“…H-bonds are mediated by interactions between light nuclei, whose motion can be influenced by nuclear quantum effects (NQEs) such as zero-point energy and quantum dispersion. It is well established that in order to accurately model the structure, thermodynamics and dynamics of H-bonded systems, the quantum-mechanical nature not only of the electrons but also of the nuclear motion must be accounted for 41,[45][46][47] . Nuclear quantum effects have been shown to affect proton disordering in high-pressure portlandite 48 , and to some extent NQEs have been accounted for in clays by applying zero-point corrections to the calculated ground-state energy 49,50 .…”

Section: Introductionmentioning

confidence: 99%

Hydrogen-bonding and nuclear quantum effects in clays

Kurapothula

Shepherd

Wilkins

2022

The Journal of Chemical Physics

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Hydrogen bonds are of paramount importance in the chemistry of clays, mediating the interaction between the clay surface and water, and for some materials between separate layers. It is well-established that the accuracy of a computational model for clays depends on the level of theory at which the electronic structure is treated. However, for hydrogen-bonded systems, the motion of light H nuclei on the electronic potential energy surface is often affected by quantum delocalization. Using path integral molecular dynamics, we show that nuclear quantum effects lead to a relatively small change in the structure of clays, but one that is comparable to the variation incurred by treating the clay at different levels of electronic structure theory. Accounting for quantum effects weakens the hydrogen bonds in clays, with H-bonds between different layers of the clay affected more than those within the same layer; this is ascribed to the fact that the confinement of an H atom inside a layer is independent of its participation in hydrogen-bonding. More importantly, the weakening of hydrogen bonds by nuclear quantum effects causes changes in the vibrational spectra of these systems, significantly shifting the O–H stretching peaks and meaning that in order to fully understand these spectra by computational modeling, both electronic and nuclear quantum effects must be included. We show that after reparameterization of the popular clay forcefield CLAYFF, the O–H stretching region of their vibrational spectra better matches the experimental one, with no detriment to the model’s agreement with other experimental properties.

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Section: Introductionmentioning

confidence: 99%

Hydrogen-bonding and nuclear quantum effects in clays

Kurapothula

Shepherd

Wilkins

2022

The Journal of Chemical Physics

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“…For instance, Cahli ́k et al revealed the significance of concerted proton tunneling in H-bonded organic molecular chains, which enhances the mechanical stability of the chains and induces the formation of electronic in-gap states localized at the ends. 79 In addition to proton tunneling, the quantum motion of H nuclei could also influence the H-bonding network topography and H-bonding strength because of the anharmonic character of the potential well. The magnitude of proton delocalization is strongly dependent on the nearest-neighboring water−water (O−O) distance.…”

Section: Atomic-scale Assessment Of Nqesmentioning

confidence: 99%

“…For instance, Cahlík et al. revealed the significance of concerted proton tunneling in H-bonded organic molecular chains, which enhances the mechanical stability of the chains and induces the formation of electronic in-gap states localized at the ends …”

Section: Probing Interfacial Water and Ice With Submolecular Resolutionmentioning

confidence: 99%

Submolecular Insights into Interfacial Water by Hydrogen-Sensitive Scanning Probe Microscopy

Guo

Jiang

2022

Acc. Chem. Res.

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Conspectus Water–solid interfaces have attracted extensive attention because of their crucial roles in a wide range of chemical and physical processes, such as ice nucleation and growth, dissolution, corrosion, heterogeneous catalysis, and electrochemistry. To understand these processes, enormous efforts have been made to obtain a molecular-level understanding of the structure and dynamics of water on various solid surfaces. By the use of scanning probe microscopy (SPM), many remarkable structures of H-bonding networks have been directly visualized, significantly advancing our understanding of the delicate competition between water–water and water–solid interactions. Moreover, the detailed dynamics of water molecules, such as diffusion, clustering, dissociation, and intermolecular and intramolecular proton transfer, have been investigated in a well-controlled manner by tip manipulation. However, resolving the submolecular structure of surface water has remained a great challenge for a long time because of the small size and light mass of protons. Discerning the position of hydrogen in water is not only crucial for the accurate determination of the structure of H-bonding networks but also indispensable in probing the proton transfer dynamics and the quantum nature of protons. In this Account, we focus on the recent advances in the H-sensitive SPM technique and its applications in probing the structures, dynamics, and nuclear quantum effects (NQEs) of surface water and ion hydrates at the submolecular level. First, we introduce the development of high-resolution scanning tunneling microscopy/spectroscopy (STM/S) and qPlus-based atomic force microscopy (qPlus-AFM), which allow access to the degrees of freedom of protons in both real and energy space. qPlus-AFM even allows imaging of interfacial water in a weakly perturbative manner by measuring the high-order electrostatic force between the CO-terminated tip and the polar water molecule, which enables the subtle difference of OH directionality to be discerned. Next we showcase the applications of H-sensitive STM/AFM in addressing several key issues related to water–solid interfaces. The surface wetting behavior and the H-bonding structure of low-dimensional ice on various hydrophilic and hydrophobic solid surfaces are characterized at the atomic scale. Then we discuss the quantitative assessment of NQEs of surface water, including proton tunneling and quantum delocalization. Moreover, the weakly perturbative and H-sensitive SPM technique can be also extended to investigations of water–ion interactions on solid surfaces, revealing the effect of hydration structure on the interfacial ion transport. Finally, we provide an outlook on the further directions and challenges for SPM studies of water–solid interfaces.

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“…In addition, considering the role of nuclear quantum effects such as zero-point motion, we conclude that the N/H/N hydrogen bond observed in the AAT-PMP neutron structure can be classied both as an LBHB and as a charge-assisted hydrogen bond. 32,33 Fig. 7 Proposed mechanism for the first half-reaction of AAT based on observations from neutron structures.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%