Magnetic Circular Dichroism of Naphthalene Derivatives: A Coupled Cluster Singles and Approximate Doubles and Time-Dependent Density Functional Theory Study

The UV-vis absorption and magnetic circular dichroism spectra of naphthalene and some of its derivatives have been simulated at the Coupled Cluster Singles and Approximate Doubles (CC2) level of theory, and at the Time-Dependent Density Functional Theory (TD-DFT) level using the B3LYP and CAM-B3LYP functionals. DFT and CC2 predict in general opposite energetic ordering of the L-b and L-a transitions (in gas phase), as previously observed in adenine. The CC2 simulations of UV and MCD spectra show the best agreement with the experimental data. Analysis of the Cartesian components of the electric dipole transition strengths and the magnetic dipole transition moment between the excited states have been considered in the interpretation of the electronic transitions and the Faraday B term inversion among the naphthalene derivatives.

Automated summary

UV-vis absorption and magnetic circular dichroism spectra of naphthalene and its derivatives were simulated using CC2 and TD-DFT methods. CC2 simulations showed the best agreement with experimental data. Analysis of electric dipole and magnetic dipole transition moments helped interpret electronic transitions and Faraday B term inversion among naphthalene derivatives.