First Principle Calculations of the Electronic and Vibrational Properties of the 3‑(1,1-Dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole Molecule

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 119; no. 8; pp. 1347 - 1358
• Main Authors: Makowska-Janusik, Malgorzata, Kajzar, Francois, Miniewicz, Andrzej, Mydlova, Lucia, Rau, Ileana
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26.02.2015
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp510102q

Results of first principle quantum chemical calculations of electronic and vibrational properties of the push–pull 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DCNP) molecule are reported and discussed. The structure of DCNP was optimized with HF/6-311G methodology and found to be planar. On the basis of obtained geometry, infrared absorption and Raman spectra were computed within the HF/6-311++G** formalism. They allow to conclude that the changes of molecule dipole moment and variation of its polarizability appear at the same vibrational mode and affect the optical properties of the DCNP. Four different methodologies: time-dependent HF and time-dependent DFT method with B3LYP, LC-BLYP, and CAM-B3LYP potentials were used to compute the optical absorption spectra of DCNP. Influence of solvent on molecular electronic structure was studied within the C-PCM model. It predicts the DFT/B3LYP methodology as the best one to compute the NLO properties of the DCNP. The computed HOMO and LUMO orbitals show evidence that the ground state of the molecule is located at its aromatic part. The discussion of charge transfer during the excitation process for the transition S0-S1 was performed. The charge transfer parameter calculated in vacuum and in solvent gives the evidence that the solvent environment weakly enhance the molecular charge transfer. It confirms the tendency of an occurrence of the intermolecular charge transfer in DCNP which is crucial for its hyperpolarizability magnitude. It was proved that the second-order susceptibility corresponding to SHG may be calculated for host–guest polymer/DCNP composite using the simple oriented gas model and the rigorous local field approach should not necessarily be applied.