TY - JOUR

T1 - Deconstructing ¹H NMR Chemical Shifts in Strong Hydrogen Bonds: A Computational Investigation of Solvation, Dynamics, and Nuclear Delocalization Effects

AU - Капланский, Марк Валерьевич

AU - Шитов, Даниил Алексеевич

AU - Толстой, Петр Михайлович

AU - Тупикина, Елена Юрьевна

PY - 2025/5/26

Y1 - 2025/5/26

N2 - This study provides the first quantitative dissection of the factors influencing 1H NMR chemical shifts δH in strong hydrogen-bonded systems, focusing on solvation, nuclear dynamics, and nuclear delocalization. A novel computational framework was developed, combining static quantum chemical calculations (nonrelativistic and relativistic), ab initio molecular dynamics (AIMD), and three-dimensional numerical solutions of the Schrödinger equation. This multiscale approach was applied to three model systems: the bifluoride anion (FHF)−, the Zundel cation (H5O2)+, and the pyridine-pyridinium cation (PyHPy)+. Our results reveal that nuclear dynamics and delocalization are the dominant factors determining δH in complexes with short, strong hydrogen bonds. Solvation effects, while critical for defining the hydrogen-bonding environment, play a secondary role. By isolating the contributions of each factor, we demonstrate that traditional methods often underestimate the quantum mechanical nature of the proton. The application of three-dimensional Schrödinger equation solutions represents a significant methodological advancement, enabling deeper insights into proton behavior in hydrogen bonds. This work not only enhances our understanding of NMR parameters in challenging systems but also establishes a robust framework for modeling complex interactions in chemical and biological environments.

AB - This study provides the first quantitative dissection of the factors influencing 1H NMR chemical shifts δH in strong hydrogen-bonded systems, focusing on solvation, nuclear dynamics, and nuclear delocalization. A novel computational framework was developed, combining static quantum chemical calculations (nonrelativistic and relativistic), ab initio molecular dynamics (AIMD), and three-dimensional numerical solutions of the Schrödinger equation. This multiscale approach was applied to three model systems: the bifluoride anion (FHF)−, the Zundel cation (H5O2)+, and the pyridine-pyridinium cation (PyHPy)+. Our results reveal that nuclear dynamics and delocalization are the dominant factors determining δH in complexes with short, strong hydrogen bonds. Solvation effects, while critical for defining the hydrogen-bonding environment, play a secondary role. By isolating the contributions of each factor, we demonstrate that traditional methods often underestimate the quantum mechanical nature of the proton. The application of three-dimensional Schrödinger equation solutions represents a significant methodological advancement, enabling deeper insights into proton behavior in hydrogen bonds. This work not only enhances our understanding of NMR parameters in challenging systems but also establishes a robust framework for modeling complex interactions in chemical and biological environments.

UR - https://www.mendeley.com/catalogue/89b7bc08-a375-3757-b86f-5f84ea48f1ee/

U2 - 10.1021/acs.jcim.5c00566

DO - 10.1021/acs.jcim.5c00566

M3 - Article

VL - 65

SP - 5019

EP - 5034

JO - Journal of Chemical Information and Modeling

JF - Journal of Chemical Information and Modeling

SN - 1549-9596

IS - 10

M1 - 10

ER -