Solute–Solvent Charge-Transfer Excitations and Optical Absorption of Hydrated Hydroxide from Time-Dependent Density-Functional Theory

• Published in: Journal of chemical theory and computation Vol. 10; no. 6; pp. 2465 - 2470
• Main Authors: Opalka, Daniel, Sprik, Michiel
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.06.2014
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/ct5002889

The electronic structure of simple hydrated ions represents one of the most challenging problems in electronic-structure theory. Spectroscopic experiments identified the lowest excited state of the solvated hydroxide as a charge-transfer-to-solvent (CTTS) state. In the present work we report computations of the absorption spectrum of the solvated hydroxide ion, treating both solvent and solute strictly at the same level of theory. The average absorption spectrum up to 25 eV has been computed for samples taken from periodic ab initio molecular dynamics simulations. The experimentally observed CTTS state near the onset of the absorption threshold has been analyzed at the generalized-gradient approximation (GGA) and with a hybrid density-functional. Based on results for the lowest excitation energies computed with the HSE hybrid functional and a Davidson diagonalization scheme, the CTTS transition has been found 0.6 eV below the first absorption band of liquid water. The transfer of an electron to the solvent can be assigned to an excitation from the solute 2pπ orbitals, which are subject to a small energetic splitting due to the asymmetric solvent environment, to the significantly delocalized lowest unoccupied orbital of the solvent. The distribution of the centers of the excited state shows that CTTS along the OH– axis of the hydroxide ion is avoided. Furthermore, our simulations indicate that the systematic error arising in the calculated spectrum at the GGA originates from a poor description of the valence band energies in the solution.