Cálculo ab initio de intensidades Raman dinâmicas utilizando a teoria da resposta linear

In this paper a methodology for the computation of Raman scattering cross-sections and depolarization ratios within the Placzek Polarizability Theory is described. The polarizability gradients are derived from the values of the dynamic polarizabilities computed at the excitation frequencies using ab initio Linear Response Theory. A sample application of the computational program, at the HF, MP2 and CCSD levels of theory, is presented for H2O and NH3. The results show that high correlated levels of theory are needed to achieve good agreement with experimental data.

Estudo teórico das transições eletrônicas usando métodos simples e sofisticados

In this paper, the use of both simple and sophisticated models in the study of electronic transitions was explored for a set of molecular systems: C2H4, C4H4, C4H6, C6H6, C6H8, "C8", C60, and [H2NCHCH(CHCH)kCHNH2]+, where k = 0 to 4. The simple model of the free particle (1D, 2D, and 3D boxes, rings or spherical surfaces), considering the boundary conditions, was found to yield similar results to the sophisticated theoretical methods such as EOM-CCSD/6-311++G** or TD(NStates=5,Root=1)-M06-2X/6-311++G**.

Covalent anion of Li(HF)3- system: an ab initio study

In this paper, we report the stability of the Li(HF)3- molecular anion calculated at the MP2/6-31++G** and CCSD(T)/6-31++G** level of theory. Five possible conformers of Li(HF)3- molecular anions have been determined employing ab initio MP2 method with 6-31++G** basis set. The most stable conformer of five Li(HF)3- anions is in a cyclic ring structure Li(HF)3-(1). From our calculations we show that the molecule is stable towards electron attachment, with an electron adiabatic electron affinity (AEA) of 199.5 meV (233.1 meV with zero point energy correction) and 471.3 meV at the MP2 and CCSD(T) levels, respectively. In addition we present vertical detachment energies of 230.2 meV and 795.8 meV at the MP2, CCSD(T), respectively. The importance of the latter has to do with the ability of experimental detection of this value.