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This study reports the spectroscopic characterization and second hyperpolarizability of the odd spin states of acetonitrile at B3LYP/aug-cc-pVDZ level of theory. The spectroscopic parameters studied in gas phase and water solvent. Upon changes of spin states of acetonitrile significant changes are observed in the spectroscopic study. Natural transition orbitals (NTOs) study also reported for acetonitrile in gas phase and water solvent. From nonlinear optical study it is observed that second hyperpolarizability of odd spin states of acetonitrile are more responsive than the first hyperpolarizability. [Display omitted] • Spectroscopic study of odd spin state of acetonitrile in gas and water solvent reported. • The solvent effect taken in to the consideration for the study using IEFPCM model. • The Natural transition orbital studied for the acetonitrile in gas phase and in water solvent. • An increase in field strength decreases the HOMO to LUMO gap in gas and solvent acetonitrile. • Thorough nlo study confirmed acetonitrile is more responsive to 2nd hyperpolarizability than 1st. The present study reports the spectroscopic characterization and second hyperpolarizability of odd spin states of acetonitrile in gas phase and water solvent. The odd spin states of acetonitrile are singlet, triplet and quintet spin state of acetonitrile have been considered for the study. The spectroscopic characterization viz. energy, geometrical parameters, infrared and electronic absorption spectra, molecular orbitals (MOs) their energies and natural transitions orbitals (NTOs) in gas phase and water solvent state reported at B3LYP/aug-cc-pVDZ level of theory. The second hyperpolarizability values are obtained using various methods and basis sets for comparison. It has been observed that the second hyperpolarizability values for the odd spin states of acetonitrile are more positive than the first hyperpolarizability. It is clearly seen that the effect of spin on spectroscopic parameters except on energy. The singlet gas phase acetonitrile calculations are well matching with the available experimental determinations. The TDDFT approach has been used to study electronic absorption spectra of all spin states of acetonitrile in gas phase and in water solvent. The IEFPCM model implemented in studying acetonitrile in water solvent at B3LYP/aug-cc-pVDZ level of theory. It is observed that HOMO to LUMO gap is larger for singlet than the triplet and quintet spin state and it decrease with an increase in strength of an applied field. All these calculations performed using Gaussian 16 program package. [ABSTRACT FROM AUTHOR]

Abstract: Vibrational and electronic spectral measurements were made for 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Optimized geometrical structure and harmonic vibrational frequencies were computed by DFT(B3LYP, CAMB3LYP, B3P86, M062X, mPW3PBE and PBE1PBE) using 6-311++G(d,p) basis set. Complete assignments of the observed spectra were proposed. The absorption spectra of the compound were computed both in gas-phase and in CH2Cl2 solution using TDCAMB3LYP/6-311++G(d,p) and PCM-TDCAMB3LYP/6-311++G(d,p) approaches, respectively, the calculated results provide a good description of positions of the bands maxima in the observed electronic spectrum. [Copyright &y& Elsevier]

Abstract: Vibrational spectral measurements were made for 1,5-dimethyl-2-phenyl-4-[(pyridin-4-ylmethylene)-amino]-1,2-dihydro-pyrazol-3-one (DPPDP). Optimized geometrical structure and harmonic vibrational frequencies were computed by ab initio RHF and DFT (B-based BP86, BLYP, BPW91, B3-based B3P86, B3LYP, B3PW91 and O3-based O3LYP) methods using 6-311++G(d,p) basis set. Complete assignments of the observed spectra were proposed. The equilibrium geometries computed by all of the methods, were compared with X-ray diffraction results. The absorption spectra of the title compound were computed both in gas phase and in CH3CN solution using TD-B3LYP/6-311++G(d,p) and PCM-B3LYP/6-311++G(d,p) approaches and the calculated results provide a good description of positions of the two band maxima in the observed electronic spectrum. [ABSTRACT FROM AUTHOR]