Nasarul Islam

Elucidation of molecular interactions between a DBU based protic ionic liquid and organic solvents: thermophysical and computational studies

Precise determination of thermodynamic properties of binary mixtures containing ionic liquids (ILs), plays an important role in process design and potential engineering applications of these mixtures. Thermodynamic studies can provide an insight into the nature of intermolecular interactions occurring between the solute and solvent in solutions. In this regard, thermodynamic properties of 1,8-diazabicyclo[5.4.0]undec-7-en-8-ium trifluoroacetate [DBUTFA] in two organic solvents viz. N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) have been evaluated at different temperatures (293.15 to 328.15) K. Apparent molar property data were fitted to a Redlich–Mayer type of equation to compute infinite dilution values and empirical parameters. The experimental studies suggest that the nature of the interactions between DBUTFA and organic solvents are influenced by temperature. DBUTFA interacts more strongly with DMF at low temperature ( 308.15 K). Density functional level of theory (DFT) was employed to investigate intra-ionic and inter-ionic interactions between the ions of PIL and organic solvents. The computational results are in good agreement with experimental results.

Computational Studies on Optoelectronic and Nonlinear Properties of Octaphyrin Derivatives

The electronic and nonlinear optical (NLO) properties of octaphyrin derivatives were studied by employing the DFT/TDFT at CAM-B3LYP/6-311++G (2d, 2p) level of the theory. Thiophene, phenyl, methyl and cyano moieties were substituted on the molecular framework of octaphyrin core, in order to observe the change in optoelectronic and nonlinear response of these systems. The frontier molecular orbital studies and values of electron affinity reveals that the studied compounds are stable against the oxygen and moisture present in air. The calculated ionization energies, adiabatic electron affinity and reorganization energy values indicate that octaphyrin derivatives can be employed as effective n-type material for Organic Light Emitting Diodes (OLEDs). This character shows an enhancement with the introduction of an electron withdrawing group in the octaphyrin framework. The polarizability and hyperpolarizability values of octaphyrin derivatives demonstrate that they are good candidates for NLO devices. The nonlinear response of these systems shows enhancement on the introduction of electron donating groups on octaphyrin moiety. However, these claims needs further experimental verification.

Investigation of comparative shielding of Morin against oxidative damage by radicals: A DFT study

Abstract This article describes theoretical study of comparative radical scavenging activity of polyphenolic flavonoid (Morin). The molecular and electronic characteristics have been computed using density functional theory approach with B3PW91/6-31G (d,p) and B3PW91/6–311G (d,p) levels of theory. The computational calculation of bond dissociation enthalpy magnitudes for all the OH sites clearly represents the frequent abstraction of proton from OH site adjacent to carbonyl groups on B ring. The molecular descriptors and frontier molecular studies confirm the higher reactivity of B and C rings as compared to A-ring of the studied flavonoid molecule.

Geometrical structure and nonlinear response variations of metal (M = Ni2+, Pd2+, Pt2+) octaphyrin complex derivatives: A DFT study

Abstract Nonlinear optical response of designed organometallic complexes of Ni2+, Pd2+, and Pt2+ metal ions with octaphyrin (OP) as ligand were explored by using DFT at CAM-B3LYP/6–311G++(d, p)/LANL2DZ/DEF2SV level of theory. The geometries of these organometallic complexes were studied in terms of effect on molecular framework by metal ion and substituent groups. The optimized geometry of free ligand displays that one of the four pyrrole rings orients out of plane to reduce the steric hindrance. The effect of the substituents on the geometry was found more prominent in the Ni2+-OP complexes. The calculations reveal enhancement in the values of dipole moment and hyperpolarizability on introducing electron withdrawing and electron donating groups in ligand framework with maximum enhancement in case of Pt2+-OP derivatives. In this study no regular trend was observed for the HOMO and LUMO energies with the second-order hyperpolarizability of M2+-OP complexes. However, we have observed that the excited-state properties calculated by using TD-DFT correlate well with the second-order hyperpolarizability values and the dependence was rationalized in terms of two-level model. Thus, from overall calculations we have observed that the designed organometallic complexes display higher polarizability and hyperpolarizability values and can be effective candidates for nonlinear response.