*J Chem Phys ; 150(21): 214102, 2019 Jun 07.*

##### RESUMO

In this work, we describe how Resonant Raman (RR) spectra can be predicted with good accuracy using the path integral formulation for the harmonic oscillator, including the Herzberg-Teller and Duschinsky rotation effects. In particular, we will focus on approximations to make these calculations more efficient and expand the current methodology to include overtones and combination bands in the final prediction. After outlining the theory, we explain how it can be made into a black-box method and discuss the approximations that rely on its intrinsic parameters. It is shown that the latter can improve the efficiency by orders of magnitude, without substantial loss in accuracy. We will also show that the predicted RR spectra are in good agreement with experiment for both the intensity and position of spectral peaks, even for higher order vibronic excitations. Thus, the method proposed here can be used as a computational aid to experiments to improve the quality of analysis and theoretical understanding of RR.

*J Chem Theory Comput ; 15(3): 1896-1904, 2019 Mar 12.*

##### RESUMO

In this work, we present a general method for predicting phosphorescence rates and spectra for molecules using time-dependent density functional theory (TD-DFT) and a path integral approach for the dynamics that relies on the harmonic oscillator approximation for the nuclear movement. We first discuss the theory involved in including spin-orbit coupling (SOC) among singlet and triplet excited states and then how to compute the corrected transition dipole moments and phosphorescence rates. We investigate the dependence of these rates on some TD-DFT parameters, such as the nature of the functional, the number of roots, and the Tamm-Dancoff approximation. After that, we evaluate the effect of different SOC integral schemes and show that our best method is applicable to a large number of systems with different excited state characters.

*J Chem Phys ; 148(3): 034104, 2018 Jan 21.*

##### RESUMO

In this work, we present and implement the theory for calculating fluorescence rates and absorption and emission spectra from first principles, using the path integral approach. We discuss some approximations and modifications to the full set of equations that improve speed and numerical stability for the case when a large number of modes are considered. New methods to approximate the excited state potential energy surface are also discussed and it is shown that for most purposes, these can be used instead of a full geometry optimization to obtain the rates mentioned above. A few examples are presented and the overall performance of the method is discussed. It is shown that the rates and spectra computed in this way are well within the acceptable range of errors and can be used in future predictions, particularly for screening purposes, with the only limitation on size being that of the electronic structure calculation itself.

*Inorg Chem ; 55(9): 4457-69, 2016 05 02.*

##### RESUMO

Regularities among electronic configurations for common oxidation states in lanthanide complexes and the low involvement of f orbitals in bonding result in the appearance of several periodic trends along the lanthanide series. These trends can be observed on relatively different properties, such as bonding distances or ionization potentials. Well-known concepts like the lanthanide contraction, the double-double (tetrad) effect, and the similar chemistry along the lanthanide series stem from these regularities. Periodic trends on structural and spectroscopic properties are examined through complete active space self-consistent field (CASSCF) followed by second-order N-electron valence perturbation theory (NEVPT2) including both scalar relativistic and spin-orbit coupling effects. Energies and wave functions from electronic structure calculations are further analyzed in terms of ab initio ligand field theory (AILFT), which allows one to rigorously extract angular overlap model ligand field, Racah, and spin-orbit coupling parameters directly from high-level ab initio calculations. We investigated the elpasolite Cs2NaLn(III)Cl6 (Ln(III) = Ce-Nd, Sm-Eu, Tb-Yb) crystals because these compounds have been synthesized for most Ln(III) ions. Cs2NaLn(III)Cl6 elpasolites have been also thoroughly characterized with respect to their spectroscopic properties, providing an exceptionally vast and systematic experimental database allowing one to analyze the periodic trends across the lanthanide series. Particular attention was devoted to the apparent discrepancy in metal-ligand covalency trends between theory and spectroscopy described in the literature. Consistent with earlier studies, natural population analysis indicates an increase in covalency along the series, while a decrease in both the nephelauxetic (Racah) and relativistic nephelauxetic (spin-orbit coupling) reduction with increasing atomic number is calculated. These apparently conflicting results are discussed on the basis of AILFT parameters. The AILFT derived parameters faithfully reproduce the underlying multireference electronic structure calculations. The remaining discrepancies with respect to experimentally derived data are mostly due to underestimation of the ligand field splittings, while the dynamic correlation and nephelauxetic effects appears to be adequately covered by CASSCF/NEVPT2.

*J Am Chem Soc ; 135(15): 5726-39, 2013 Apr 17.*

##### RESUMO

The Mn(IV)3CaO4 cubane is a structural motif present in the oxygen-evolving complex (OEC) of photosystem II and in water-oxidizing Mn/Ca layered oxides. This work investigates the magnetic and spectroscopic properties of two recently synthesized complexes and a series of idealized models that incorporate this structural unit. Magnetic interactions, accessible spin states, and (55)Mn isotropic hyperfine couplings are computed with quantum chemical methods and form the basis for structure-property correlations. Additionally, the effects of oxo-bridge protonation and one-electron reduction are examined. The calculated properties are found to be in excellent agreement with available experimental data. It is established that all synthetic and model Mn(IV)3CaO4 cubane complexes have the same high-spin S = (9)/2 ground state. The magnetic coupling conditions under which different ground spin states can be accessed are determined. Substitution of Mn(IV) magnetic centers by diamagnetic ions [e.g., Ge(IV)] allows one to "switch off" specific spin sites in order to examine the magnetic orbitals along individual Mn-Mn exchange pathways, which confirms the predominance of ferromagnetic interactions within the cubane framework. The span of the Heisenberg spin ladder is found to correlate inversely with the number of protonated oxo bridges. Energetic comparisons for protonated models show that the tris-µ-oxo bridge connecting only Mn ions in the cubane has the lowest proton affinity and that the average relaxation energy per additional proton is on the order of 18 kcal·mol(-1), thus making access to ground states other than the high-spin S = (9)/2 state in these cubanes unlikely. The relevance of these cubanes for the OEC and synthetic oxides is discussed.