title: Adsorption and trace detection of pharmacologically significant 5-methylthio-1, 3, 4-thiadiazole-2-thiol molecule adsorbed on silver nanocolloids and understanding the role of Albrecht's "A" and Herzberg-Teller contributions in the SERS spectra.
abstract: The surface enhanced Raman scattering (SERS) spectra of biologically and industrially significant 5-methylthio-1, 3, 4-thiadiazole 2-thiol molecule have been investigated. The SERS spectra at various concentrations of the adsorbate are compared with the Fourier transform Infrared (FTIR) and normal Raman spectra (NRS) of the probe molecule recorded in different environmental conditions. The optimized molecular structures of the most probable thione and the thiol forms of the molecule have been estimated from the density functional theory (DFT) calculations. The vibrational signatures of the molecule have been assigned from the potential energy distributions (PEDs). The detail vibrational analyses reveal that ∼54% of the thione form of the molecule is prevalent in the solid state and its population increases to ∼65% in ACN solvent medium. Concentration dependent SERS, together with the 2-dimensional correlation spectra (2D-COS), corroborate the presence of both the thione and the thiol forms of the molecule even in the surface adsorbed state. The orientations of the thione and the thiol forms of the molecule on the nanocolloidal silver surface have been predicted from the surface selection rule. The selective enhancement of Raman bands in the SERS spectra have been explored from the view of the Albrecht's "A" and Herzberg-Teller (HT) charge transfer (CT) contribution.
authors.affiliation: Department of Physics, Sammilani Mahavidyalaya, Baghajatin Station, E.M. Bypass, Kolkata 700075, India. Electronic address: joydeep72_c@rediffmail.com.
authors.forename: Joydeep
authors.initials: J
authors.lastname: Chowdhury
authors.affiliation: Department of Physics, Victoria Institution (College), 78 B, A.P.C. Road, Kolkata 700009, India.
authors.forename: Subhendu
authors.initials: S
authors.lastname: Chandra
authors.affiliation: Department of Spectroscopy, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032, India.
authors.forename: Manash
authors.initials: M
authors.lastname: Ghosh
mesh_terms: D000327:Adsorption; D003102:Colloids / Q000737:chemistry*; D004583:Electrons; D006863:Hydrogen-Ion Concentration; D008958:Models, Molecular; D008968:Molecular Conformation; D053758:Nanoparticles / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D013438:Sulfhydryl Compounds / Q000032:analysis*; D013696:Temperature; D013830:Thiadiazoles / Q000032:analysis*; D014732:Vibration
chemical_list: C000598814:5-methylthio-1,3,4-thiadiazole-2-thiol; D003102:Colloids; D012997:Solvents; D013438:Sulfhydryl Compounds; D013830:Thiadiazoles; D012834:Silver
keywords: 5-Methylthio-1, 3, 4-thiadiazole 2-thiol; Albrecht’s “A” and Herzberg–Teller (HT); Charge transfer (CT); FTIR; Raman; SERS