Optical Activity of Spin-Forbidden Electronic Transitions in Metal Complexes from Time-Dependent Density Functional Theory with Spin-Orbit Coupling.

The calculation of magnetic transition dipole moments and rotatory strengths was implemented at the zeroth-order regular approximation (ZORA) two-component relativistic time-dependent density functional theory (TDDFT) level. The circular dichroism of the spin-forbidden ligand-field transitions of tris(ethylenediamine)cobalt(III) computed in this way agrees very well with available measurements. Phosphorescence dissymmetry factors and the corresponding lifetimes are evaluated for three N-heterocyclic-carbene-based iridium complexes, two of which contain helicene moieties, and for two platinahelicenes.

Comparative Study of Vibrational Raman Optical Activity with Different Time-Dependent Density Functional Approximations: The VROA36 Database.

A new database, VROA36, is introduced to investigate the performance of computational approaches for vibrational Raman optical activity (VROA) calculations. The database is composed of 36 molecules with known experimental VROA spectra. It includes 93 conformers.

Validation of microscopic magnetochiral dichroism theory.

Magnetochiral dichroism (MChD), a fascinating manifestation of the light-matter interaction characteristic for chiral systems under magnetic fields, has become a well-established optical phenomenon reported for many different materials. However, its interpretation remains essentially phenomenological and qualitative, because the existing microscopic theory has not been quantitatively confirmed by confronting calculations based on this theory with experimental data. Here, we report the experimental low-temperature MChD spectra of two archetypal chiral paramagnetic crystals taken as model systems, tris(1,2-diaminoethane)nickel(II) and cobalt(II) nitrate, for light propagating parallel or perpendicular to the axis of the crystals, and the calculation of the MChD spectra for the Ni(II) derivative by state-of-the-art quantum chemical calculations.

Ab Initio Study of Vibronic and Magnetic 5f-to-5f and Dipole-Allowed 5f-to-6d and Charge-Transfer Transitions in [UX] (X = Cl, Br; = 1, 2).

The absorption spectra of the octahedral [UX] (X = Cl, Br; = 1, 2) complexes in the near-infrared (NIR) and UV-vis spectral regions were studied theoretically, using a relativistic restricted active space second-order perturbation theory (RASPT2) wavefunction framework, with the spin-orbit (SO) coupling treated by state interaction, in conjunction with Kohn-Sham density functional theory calculations for determining the vibrational normal modes. The electric-dipole-allowed ligand-to-metal charge-transfer (LMCT) and 5f-to-6d transitions, and the electric-dipole-forbidden 5f-to-5f ligand field (LF) transitions, are thereby obtained within the same theoretical framework. For the 5f-to-5f LF transitions, the observed absorption intensity is mostly due to vibronic coupling with low-energy electric-dipole-allowed transitions, but in some cases, the magnetic dipole intensity of the purely electronic transition has comparable intensity to the vibronic transitions.

Theoretical study of the Raman optical activity spectra of with M = Co, Rh.

Vibrational Raman optical activity (ROA) spectra were calculated under off-resonance, near-resonance, and at-resonance conditions for (A) and under off-resonance conditions for (B) using a new driver software for calculating the ROA intensities from complex (damped) time-dependent linear response Kohn-Sham theory. The off-resonance spectra of A and B show many similarities. At an incident laser wavelength of 532 nm, used in commercial ROA spectrometers, the spectrum of A is enhanced by near-resonance with the ligand-field transitions of the complex.