Absorption Intensities of Organic Molecules from Electronic Structure Calculations versus Experiments: the Effect of Solvation, Method, Basis Set, and Transition Moment Gauge

2024/08/14 by Jorge C. Garcia-Alvarez, Samer Gozem · 1 voice
Physics and Astronomy · Chemistry · Mathematics · #Spectroscopy and Quantum Chemical Studies #Photochemistry and Electron Transfer Studies #Advanced Chemical Physics Studies #Solvation #Basis set #Moment (physics) #Basis (linear algebra) #Gauge (firearms) #Set (abstract data type) #Chemical physics #Molecule #Organic molecules #Computational chemistry #Absorption (acoustics) #Chemistry #Electronic structure #Statistical physics #Materials science #Molecular physics #Atomic physics #Physics #Computer science #Quantum mechanics #Mathematics #Organic chemistry

paper · doi:10.1021/acs.jctc.4c00642

openalex publication_date 2024/08/14 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

is a solvent refractive index factor that arises from the energy flux of the radiation field in a dielectric (solvent). Theoretical cavity field corrections considering spherical cavities do not improve the agreement between computed and experimental data. Corrections that account for the molecular shape and the direction of transition dipole moments, or that explicitly account for the effect of solvent molecules on the local field, should be more appropriate.

Citations

• Modern Quantum Mechanics
• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
• Density-functional approximation for the correlation energy of the inhomogeneous electron gas
• Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
• The Dielectric Polarization of Polar Liquids
• A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
• Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space
• Glossary of terms used in photochemistry, 3rd edition (IUPAC Recommendations 2006)
• Progress in Time-Dependent Density-Functional Theory
• Self-Consistent Equations Including Exchange and Correlation Effects

Discussions

• I think two different issues are being mixed together here: the spectral variable used in the integration, and the local-field correction. For an isotropic sample, the oscillator strength of an isolat [stackexchange, 2 points]

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• Local-field corrections to the decay rate of excited molecules in absorbing cavities: the Onsager model
• Comparison of three methods to compute optical absorption spectra of organic molecules and solids