Spectroscopy and second hyperpolarizability of odd spin states of acetonitrile: Theoretical study.

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]