Angsula Ghosh

Effect of hydrogen bond formation on the NMR properties of microhydrated ortho-aminobenzoic acid

The influence of the hydrogen bond formation on the nuclear magnetic resonance parameters has been investigated in the case of microhydrated ortho-aminobenzoic acid (o-Abz) in the gas-phase. DFT-B3LYP/aug-cc-pVDZ predicted 1H and 13C isotropic chemical shifts with respect to TMS of the isolated o-Abz are in reasonable agreement with available experimental data. The isotropic and anisotropic chemical shifts for all atoms of o-Abz within the o-Abz ··· (H2O)1-3 complexes have been calculated at the Hartree–Fock, and density functional (B3LYP) theoretical levels using the 6-31++G(2d,2p) and aug-cc-pVDZ basis sets and considering the counterpoise corrections for the basis set superposition errors. The chemical shift values of the carboxyl group atoms of microhydrated o-Abz relative to isolated o-abz do not show significant basis set dependence. Both the hydrogen and carbon atoms constituting the carboxyl group of o-Abz suffer downfield shift due to formation of hydrogen bond with water. The length of hydrogen bond formed between o-Abz and water is found to vary with the number of water molecules present around o-Abz. A direct correlation between the hydrogen bond length and isotropic chemical shift of the bridging hydrogen is observed for both C = O ··· H-O and O-H ··· O interactions.

Pressure‐induced polymorphism in nanostructured SnSe

The pressure-induced phase transitions in nanostructured SnSe were investigated using angle-dispersive X-ray diffraction in a synchrotron source along with first-principles density functional theory (DFT) calculations. The variation of the cell parameters along with enthalpy calculations for pressures up to 18 GPa have been considered. Both the experimental and the theoretical approaches demonstrate a phase transition at around 4 GPa. Below 8.2 GPa the X-ray diffraction patterns were fitted using the Rietveld method with space group Pnma (No. 62). The lattice parameters and atomic positions for the above-mentioned symmetry were used in DFT calculations of thermodynamic parameters. The enthalpy calculations with the computationally optimized structure and the proposed Pnma structure of SnSe were compatible. The variations of the cell volume for the high-pressure phases are described by a third-order Birch–Murnaghan equation of state.

Electron spin resonance in presence of a magnetic impurity in graphene

The ESR of a magnetic probe sited at a distance R from an adatom in graphene, interacting via a RKKY interaction, is studied. The spin relaxation rate of the magnetic probe in the case of pristine graphene satisfies a T(3) dependence for all temperatures at the Dirac point. However, away from the Dirac point a T(3) dependence is observed only for high temperatures unlike the Korringa behavior at low temperatures. Moreover, the zero-temperature relaxation rate of the pristine graphene demonstrates a quadratic dependence on the chemical potential. In the presence of the magnetic adatom hybridized with one site of the graphene sublattice we observe a dip in the relaxation rate away from the Dirac point. At the Dirac point a deviation from the T(3) dependence is observed. The presence of the Coulomb interaction U also modifies the zero-temperature relaxation rate when compared to that of pristine graphene. The transition from the magnetic state to the non-magnetic state is also characterized by a minimum in the relaxation rate.

Spin–spin coupling constants in linear substituted HCN clusters

ABSTRACT The indirect nuclear spin–spin coupling constants of homogeneous hydrogen-bonded HCN clusters are compared with those of inhomogeneous HCN clusters where one of the terminal HCN molecules is substituted by its isomer HNC and by LiCN. Both the intra- and intermolecular (across the hydrogen bond) coupling constants are calculated for the linear form of the clusters containing up to three molecular monomers using different hybrid DFT functionals. The geometry of the monomers and clusters is optimised at the B3LYP/6-311++G(d,p) level. The effect of substitution by the ionic compound LiCN on the coupling constants of HCN is found to be more pronounced than that by HNC. The Ramsey parameters that form the total spin–spin coupling constants are also analysed individually. Among the four Ramsey parameters, the Fermi Contact term is found to be the dominant contributor to the total coupling constants in most cases. The presence of LiCN in the cluster tends to decrease the intramolecular Fermi Contact values, while HNC increases the same in all dimers and trimers. The contributions of localised molecular orbitals have been analysed for the HCN–HNC cluster to obtain some additional insight about the SSCC transmission mechanism along the coupling pathway. GRAPHICAL ABSTRACT

NMR spin–spin coupling constants in microhydrated ortho-aminobenzoic acid

The influence of the hydrogen-bond formation on the NMR spin–spin coupling constants, including the Fermi contact, the diamagnetic spin–orbit, the paramagnetic spin–orbit and the spin dipole term, has been investigated for the ortho-aminobenzoic acid microhydrated with up to three water molecules. The one-bond and two-bond spin–spin coupling constants for several intra-molecular and across-the-hydrogen-bond atomic pairs are calculated employing high-level density functional theory in combination with the B3LYP functional with two different types of extended basis sets for each level of microhydration. The spin–spin coupling constants, in general, vary inversely with the hydrogen bond length. The Fermi contact term is found to be the dominant contributor to the total value of spin–spin coupling constant followed by the paramagnetic spin–orbit term. The variations of Fermi contact term and atomic charge distribution with size of microhydration follow quite similar trend. The effect of explicit solvation provided by microhydration has also been compared briefly with that of bulk implicit solvation obtained through polarised continuum model and mixed microhydration/continuum approach.