title: Picosecond solvation dynamics--a potential viewer of DMSO-water binary mixtures.
abstract: In this work, we have investigated the composition dependent anomalous behavior of dimethyl sulfoxide (DMSO)-water binary mixture by collecting the ultrafast solvent relaxation response around a well known solvation probe Coumarin 480 (C480) by using a femtosecond fluorescence up-conversion spectrometer. Recent molecular dynamics simulations have predicted two anomalous regions of DMSO-water binary mixture. Particularly, these studies encourage us to investigate the anomalies from experimental background. DMSO-water binary mixture has repeatedly given evidences of its dual anomalous nature in front of our systematic investigation through steady-state and time-resolved measurements. We have calculated average solvation times of C480 by two individual well-known methods, among them first one is spectral-reconstruction method and another one is single-wavelength measurement method. The results of both the methods roughly indicate that solvation time of C480 reaches maxima in the mole fraction of DMSO XD = 0.12-0.17 and XD = 0.27-0.35, respectively. Among them, the second region (XD = 0.27-0.35) is very common as most of the thermodynamic properties exhibit deviation in this range. Most probably, the anomalous solvation trend in this region is fully guided by the shear viscosity of the medium. However, the first region is the most interesting one. In this region due to formation of strongly hydrogen bonded 1DMSO:2H2O complexes, hydration around the probe C480 decreases, as a result of which solvation time increases.
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur, WB 721302, India.
authors: Debasis
authors: D
authors: Banik
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur, WB 721302, India.
authors: Niloy
authors: N
authors: Kundu
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur, WB 721302, India.
authors: Jagannath
authors: J
authors: Kuchlyan
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur, WB 721302, India.
authors: Arpita
authors: A
authors: Roy
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur, WB 721302, India.
authors: Chiranjib
authors: C
authors: Banerjee
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur, WB 721302, India.
authors: Surajit
authors: S
authors: Ghosh
authors: Department of Chemistry, Indian Institute of Technology, Kharagpur, WB 721302, India.
authors: Nilmoni
authors: N
authors: Sarkar
mesh_terms: D065966:Absorption, Physicochemical; D003374:Coumarins / Q000737:chemistry; D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D006860:Hydrogen Bonding; D007700:Kinetics; D011807:Quinolizines / Q000737:chemistry; D012997:Solvents / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D014867:Water / Q000737:chemistry*
chemical_list: D003374:Coumarins; D011807:Quinolizines; D012997:Solvents; D014867:Water; C573700:coumarin 480; D004121:Dimethyl Sulfoxide