Modeling absorption spectra of molecules in solution

2018/09/13 by Tim J. Zuehlsdorff, Christine M. Isborn · 116 citations
Chemistry · Engineering · Physics and Astronomy · #Absorption (acoustics) #Absorption spectroscopy #Atomic physics #Chemical physics #Chemistry #Dipole #Excitation #Excited state #Ground state #Molecular Junctions and Nanostructures #Molecular physics #Molecule #Optics #Organic chemistry #Photochemistry and Electron Transfer Studies #Physics #Quantum mechanics #Solvent #Solvent effects #Spectral line #Spectroscopy #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.1002/qua.25719

published in International Journal of Quantum Chemistry 119(1) (Wiley)

openalex publication_date 2018/09/13 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

The presence of solvent tunes many properties of a molecule, such as its ground and excited state geometry, dipole moment, excitation energy, and absorption spectrum. Because the energy of the system will vary depending on the solvent configuration, explicit solute–solvent interactions are key to understanding solution‐phase reactivity and spectroscopy, simulating accurate inhomogeneous broadening, and predicting absorption spectra. In this tutorial review, we give an overview of factors to consider when modeling excited states of molecules interacting with explicit solvent. We provide practical guidelines for sampling solute–solvent configurations, choosing a solvent model, performing the excited state electronic structure calculations, and computing spectral lineshapes. We also present our recent results combining the vertical excitation energies computed from an ensemble of solute–solvent configurations with the vibronic spectra obtained from a small number of frozen solvent configurations, resulting in improved simulation of absorption spectra for molecules in solution.

Citations

• Frozen density functional approach for ab initio calculations of solvated molecules

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