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. 2025 May 8;129(18):4077-4092.
doi: 10.1021/acs.jpca.5c01095. Epub 2025 Apr 29.

Hydrogen Bonds under Electric Fields with Quantum Accuracy

Alessandro Amadeo  1   2 , Marco Francesco Torre  2 , Klaudia Mráziková  3   4 , Franz Saija  4 , Sebastiano Trusso  4 , Jing Xie  5 , Matteo Tommasini  6 , Giuseppe Cassone  4
Affiliations

Hydrogen Bonds under Electric Fields with Quantum Accuracy

Alessandro Amadeo et al. J Phys Chem A. .

Abstract

Hydrogen bonds (H-bonds) are pivotal in various chemical and biological systems and exhibit complex behavior under external perturbations. This study investigates the structural, vibrational, and energetic properties of prototypical H-bonded dimers, water (H2O)2, hydrogen fluoride (HF)2, hydrogen sulfide (H2S)2, and ammonia (NH3)2 - and the respective monomers under static and homogeneous electric fields (EFs) using the accurate explicitly correlated singles and doubles coupled cluster method (CCSD) for equilibrium geometries and harmonic vibrational frequencies and the perturbative triples CCSD(T) method for energies. As for the vibrational response of the H2O, HF, H2S, and NH3 monomers, it turns out that dipole derivatives primarily govern the geometry relaxation. Perturbation theory including cubic anharmonicity can reproduce CCSD results on the vibrational Stark effect, except for NH3, where deviations arise due to its floppiness. The field-induced modifications in H-bond lengths, vibrational Stark effects, binding energies, and charge-transfer mechanisms in monomers and dimers are elucidated. Symmetry-adapted perturbation theory (SAPT) analysis on dimers reveals that electrostatics dominates the stabilization of H-bonds across all field strengths, while induction contributions increase significantly with stronger fields, particularly in systems with more polarizable atoms. Our results reveal a universal strengthening of intermolecular interactions at moderate to strong field intensities with significant variability among dimers due to inherent differences in molecular polarizability and charge distribution. Notably, a direct correlation is observed between the binding energies and the vibrational Stark effect of the stretching mode of the H-bond donor molecule, both in relation to the charge-transfer energy term, across all of the investigated dimers. All of these findings provide insights into the EF-driven modulation of H-bonds, highlighting implications for catalysis, hydrogen-based technologies, and biological processes.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Electric-field-induced variation relative to the zero-field case of the covalent bond length (a) and molecular angle (b) of hydrogen fluoride (green squares), water (red dots), hydrogen sulfide (yellow up-triangles), and ammonia (blue down-triangles) for various field intensities and evaluated at the CCSD/aug-cc-pVTZ theory level. Positive (negative) values of the field strength correspond to cases in which the field axis is aligned toward (against) the molecular dipole vector (see the inset in (a) for water). Vertical dotted lines separate the two distinct field-molecule arrangements here investigated.
Figure 2
Figure 2
Dipole moment (a) and ground-state energy relative to the zero-field case (b) of the investigated monomers as a function of the electric field intensity evaluated at the CCSD/aug-cc-pVTZ theory level.
Figure 3
Figure 3
Infrared vibrational Stark effect of the symmetric stretching (a) and bending (b) vibrational modes of the investigated monomers evaluated at the CCSD/aug-cc-pVTZ theory level.
Figure 4
Figure 4
Mulliken charge localized on the heteroatoms (F, O, S, N) of hydrogen fluoride (green squares), water (red dots), hydrogen sulfide (yellow triangles), and ammonia (blue triangles) for various field intensities and evaluated at the CCSD/aug-cc-pVTZ theory level.
Figure 5
Figure 5
HOMO (a) and LUMO (b) energies of hydrogen fluoride (green squares), water (red dots), hydrogen sulfide (yellow up-triangles), and ammonia (blue down-triangles) for various field intensities and evaluated at the CCSD/aug-cc-pVTZ theory level.
Figure 6
Figure 6
(a) Optimized X–H (X = F, O, S) covalent bond length of the H-bond donor molecule (D) lying on the H-bond of the investigated dimers and (b) the respective relaxed H-bond length as a function of the field strength evaluated at the CCSD/aug-cc-pVTZ theory level. In the insets, the considered molecular arrangement for the (H2O)2 moiety only and the respective plotted quantities are highlighted.
Figure 7
Figure 7
Infrared vibrational Stark effect of the symmetric stretching mode (a) of the X–H (X = F, O, S) covalent bond and bending (b) mode of the molecular species donating the H-bond in the investigated dimers (see legend) evaluated at the CCSD/aug-cc-pVTZ theory level.
Figure 8
Figure 8
Binding energy associated with the H-bond of the hydrogen fluoride (green squares), water (red dots), and hydrogen sulfide (yellow up-triangles) dimers as a function of the electric field strength and evaluated up to the Complete Basis Set (CBS) limit determined by extrapolating the results stemming from CCSD(T) energy calculations employing the aug-cc-pV[X = 2, 3, 4]Z basis sets (i.e., CCSD(T)/CBS).
Figure 9
Figure 9
CCSD/aug-cc-pVTZ electron density differences (Δρ) for various field strengths (see legends) determined by using the zero-field density and nuclear positions as a reference for the water (a), hydrogen sulfide (b), and hydrogen fluoride (c) dimers. Isocountours correspond to Δρ = +0.003 au in all cases. In the bottom panels, the Mulliken charge localized on the hydrogen atoms lying on the H-bond (d), on the H-bond donor heteroatoms (e), and on the H-bond acceptor heteroatoms (f), are shown for the hydrogen fluoride (green squares), water (red dots), and hydrogen sulfide (yellow up-triangles) dimers as a function of the electric field strength.
Figure 10
Figure 10
HOMO (a) and LUMO (b) energies of the hydrogen fluoride (green squares), water (red dots), and hydrogen sulfide (yellow up-triangles) dimers for various field intensities and evaluated at the CCSD/aug-cc-pVTZ theory level.
Figure 11
Figure 11
Dependence of the symmetry-adapted perturbation theory (SAPT) interaction energy components such as electrostatics (Elect.), exchange-repulsion (Exch.-Rep.), induction (Ind.), and London dispersion (Disp.) on the electric field intensity for water (a, b), hydrogen sulfide (c, d), and hydrogen fluoride (e, f) dimers. The left panels show absolute values of the SAPT interaction energy components while the right panels depict the contributions of the stabilizing components to the total stabilization energy of the dimers.
Figure 12
Figure 12
Relationship between binding energy (a) and symmetric stretching frequency of the H-bond donor (b) with respect to charge-transfer obtained with the SAPT2+(3)-ct/aug-cc-pVTZ for water (red), hydrogen sulfide (yellow), and hydrogen fluoride (green) dimers.
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