Quantifying plasmonic characteristics of pure and alkali doped aluminium clusters.

Study of plasmonic response of molecules and metal nanoclusters have drawn a considerable attention during recent times due to their various practical applications. In this study, the optical properties and the plasmonic response of our recently reported Al13+ cluster [Guin et al. Journal of Molecular Graphics and Modelling, 2020, 97, 107544] and its alkali doped counterparts [Guin et al. Journal of Molecular Modeling, 2021, 27, 235] have been investigated based on Transition dipole moment (TDM), Natural Transition Orbital (NTO) and transition inverse participation ratio (TIPR) indices. Recently these indices have been utilized by various scientists to characterize plasmonic transitions of molecular systems and metal nanoclusters. In TDM analysis, the magnitude of all the contributing TDMs associated with the molecular orbital transitions have been estimated along with the angles the individual dipoles make with the resultant dipole moment vector. A transition having at least two dominating TDM contributions along with phase matching indicate a collective or plasmonic transition. The collectiveness of orbital transitions is also corroborated through NTO and TIPR analysis. The effect of solvent medium on the optical properties and plasmonic transitions have also been studied using time dependent density functional theory in the conductor like polarizable continuum model (TDDFT-CPCM). The solvent has a strong impact on the optical properties as well as the plasmonic response of the clusters. The dielectric environment of the solvent red shifts and broadens the spectra with respect to that in the gas phase. Plasmon like excitations have been found for Li doped Al13+ cluster without solvent and Na doped Al13+ cluster in ethanol and THF.

Taming the excited states of butadiene, hexatriene, and octatetraene using state specific multireference perturbation theory with density functional theory orbitals.

To compute the electronic excitation energies, a state-specific multireference Møller-Plesset perturbation theory (SSMRPT) with a complete active space configuration interaction reference function constructed using the orbitals obtained by the density functional theory (DFT) is presented as an accurate, as well as computationally affordable, and efficient protocol at the level of second order. The global hybrid B3LYP (Becke, 3-parameter, Lee-Yang-Parr) functional has been used to generate orbitals. The present method, called DFT-SSMRPT, uses perturbers that are individual Slater determinants and accounts for the coupling between the nondynamical and dynamical correlation effects. We have applied the new method to compute excitation energies in conjugated systems of π-electrons such as trans-1,3-butadiene, trans,trans-1,3,5-hexatriene, and all-trans-1,3,5,7-octatetraene. The ordering of the excited states is correctly reproduced by the DFT-SSMRPT calculations. The relative ordering of low-lying excited 1Bu and 1Ag states alters when the length of the polyene changes. The results match reasonably well with the literature including experimental and best theoretical findings. The accuracy of the method is sufficient to discern the energy gap between the close low-lying singlet and triplet states. The DFT-SSMRPT appears as an affordable computational ab initio avenue for a qualitatively correct description of excitation energies.