Structure and Dynamics of ATP and the ATP–Zn²⁺ Complex in Solution

Despite the crucial role of ATP in life and artificial life-like applications, fundamental aspects relevant to its function, such as its conformational properties and its interaction with water and ions, remain unclear. Here, by integrating linear and two-dimensional infrared spectroscopy with <i>ab initio</i> molecular dynamics, we provide a detailed characterization of the vibrational spectra of the phosphate groups in ATP and in its complex with Zn²⁺ in water. Our study highlights the role of conformational disorder and solvation dynamics, beyond the harmonic normal-mode analysis, and reveals a complex scenario in which electronic and environmental effects tune the coupling between phosphate vibrations. We identify βγ-bidentate and αβγ-tridentate modes as the preferential coordination modes of Zn²⁺, as was proposed in the literature for Mg²⁺, although this conclusion is reached by a different spectral interpretation.