Puspitapallab Chaudhuri

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-Abzu2009···u2009(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 Cu2009=u2009Ou2009···u2009H-O and O-Hu2009···u2009O interactions.

Effect of hydrogen bond formation on the elastic molecular scattering: a case study with methanol

Rayleigh optical activities of small hydrogen-bonded methanol clusters containing two to five molecules are reported. For the methanol trimer, tetramer, and pentamer both cyclic and linear structures are considered. After the geometry optimizations, the dipole moments and the dipole polarizabilities (mean, interaction, and anisotropic components) are calculated using HF, MP2 and DFT (B3LYP, B3P86 and BH&HLYP) with aug-cc-pVDZ extended basis set. The polarizabilities are used to analyse the depolarization ratios and the Rayleigh scattering activities. The variations in the activity and in the depolarization for Rayleigh scattered radiation with the increase in the cluster size for both cyclic and linear structures are analysed.

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 18u2005GPa have been considered. Both the experimental and the theoretical approaches demonstrate a phase transition at around 4u2005GPa. Below 8.2u2005GPa 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.

Hydrogen-bonded glycine–HCN complexes in gas phase: structure, energetics, electric properties and cooperativity

Twelve hydrogen-bonded complexes of glycine and hydrogen cyanide have been studied using high-level quantum-chemical calculations in gas phase. In particular, six 1:1 glycine–HCN dimers and six 1:2 glycine–HCN trimers have been considered. Besides the characteristics of the hydrogen bonds and their effect on molecular structure and energetics, several molecular electric properties have been calculated utilising two different models: MP2/6-31++G(d,p) and DFT-B3LYP/6-31++G(d,p). Although the structural parameters calculated by the two models are similar, equilibrium electronic energies of the clusters show model dependence. The lowest energy dimer is same in both the models which is ca. 3.0 kcal/mol more stable than the highest energy dimer. However, the lowest energy trimer is different in two methods. The energetic difference of stability between the highest and lowest trimer is 4.2 kcal/mol (4.4 kcal/mol) at an MP2 (B3LYP) level of calculation. The bond angles of glycine, in particular, are quite sensitive to the hydrogen-bond formation. Four out of six trimers are found to be strongly cooperative in both the models. Significant changes of dipole moments and polarisabilities of isolated glycine and hydrogen cyanide are observed due to the formation of hydrogen bonding. The Rayleigh scattering intensities of all clusters are much larger than those of their constituent monomers.

Effects of microhydration on the electronic properties of ortho-aminobenzoic acid.

High-level density functional electronic structure calculations have been performed to analyze the effect of microsolvation with water on the electronic properties of ortho-aminobenzoic acid (o-Abz). The hydrogen-bonded interaction of the o-Abz molecule with one to three water molecules, o-Abz···(H2O)n (n = 1–3), has been considered in two different situations, once the solvent water molecules are placed close to the carboxyl (−COOH) group of o-Abz producing the o-Abz···[H2O]nCOOH complexes and when the water molecules are placed close to the amino (−NH2) group producing the o-Abz···[H2O]nNH2 clusters. Variation of the vibrational spectra and energetics upon hydrogen-bond formation are analyzed and compared with available experimental data. The effect of cooperativity is also analyzed. Overall, the hydrogen-bonded o-Abz···[H2O]nCOOH clusters are found to be more stable than the o-Abz···[H2O]nNH2 clusters.

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.