Photoelectron Spectra of Aqueous Solutions from First Principles

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• 作者：Alex P. Gaiduk ; Marco Govoni ; Robert Seidel ; Jonathan H. Skone ; Bernd Winter ; Giulia Galli
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：June 8, 2016
• 年：2016
• 卷：138
• 期：22
• 页码：6912-6915
• 全文大小：270K
• 年卷期：0
• ISSN：1520-5126

文摘

We present a combined computational and experimental study of the photoelectron spectrum of a simple aqueous solution of NaCl. Measurements were conducted on microjets, and first-principles calculations were performed using hybrid functionals and many-body perturbation theory at the G₀W₀ level, starting with wave functions computed in ab initio molecular dynamics simulations. We show excellent agreement between theory and experiments for the positions of both the solute and solvent excitation energies on an absolute energy scale and for peak intensities. The best comparison was obtained using wave functions obtained with dielectric-dependent self-consistent and range-separated hybrid functionals. Our computational protocol opens the way to accurate, predictive calculations of the electronic properties of electrolytes, of interest to a variety of energy problems.