The present work is a theoretical investigation on supramolecular complexes of a fullerene crown ether (A and B isomers) with a derivative of π-extended tetrathiafulvalene (T). The geometry and the electronic structure of seven different conformers of the complex of dibenzo-18-crown-6 ether of fullero-N-methylpyrrolidine with a N-benzyl-N-(4-{[9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthrac...

Multiple mechanisms of backbiting and b-scission reactions in free-radical polymerization of methyl acrylate are modeled using different levels of theory, and the rigid-rotor harmonicoscillator (RRHO) and hindered-rotor (HR) approximations. We identify the most cost-effective computational method(s) for studying the reactions and assess the effects of different factors (e.g., functional type an...

Acid–base thermochemistry of isolated amino acids containing oxygen or sulfur in their side chain (serine, threonine, cysteine and methionine) have been examined by quantum chemical computations. Density functional theory (DFT) was used, with B3LYP, B97-D and M06-2X functionals using the 6-31+G(d,p) basis set for geometry optimizations and the larger 6-311++G(3df,2p) basis set for energy comput...

We present a new formulation of variational transition state theory (VTST) called multi-structural VTST (MS-VTST) and the use of this to calculate the rate constant for the 1,4-hydrogen shift isomerization reaction of 1-pentyl radical and that for the reverse reaction. MS-VTST uses a multifaceted dividing surface and provides a convenient way to include the contributions of many structures (typ...

Opioids such as morphine are important pain-relieving drugs but also carry a risk of harmful side effects including addiction. Morphine is active in both healthy and inflamed tissue, however, decreasing the pKa biochemically-active amine group can promote selective binding more acidic conditions tissue reduce associated with opioids. Herein, we explore impact fluorination on fluoromorphine deri...

Herein we present an assessment to determine which of nine well-established DFT functionals best describes the reduction of C2H2Se2(-)˙. In addition, we have also studied the effects of changing the substituents bound to the alkene functional group of dithiolene and diselenolene ligands. Such ligands are important due to their unique electrochemical and physical properties when ligated to metal...

Mononitrobiuret (MNB) and 1,5-Dinitrobiuret (DNB) are, tetrazole-free, nitrogen-rich, energetic compounds. For the first time, the thermal decomposition mechanisms of MNB and DNB have been investigated by advanced ab initio kinetics theories. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for MNB, DNB, and ...