Rumpa Pal

Towards crystal structure prediction of complex organic compounds – a report on the fifth blind test

The results of the fifth blind test of crystal structure prediction, which show important success with more challenging large and flexible molecules, are presented and discussed.

Conformation-Changing Aggregation in Hydroxyacetone: A Combined Low-Temperature FTIR, Jet, and Crystallographic Study

Aggregation in hydroxyacetone (HA) is studied using low-temperature FTIR, supersonic jet expansion, and X-ray crystallographic (in situ cryocrystallization) techniques. Along with quantum chemical methods (MP2 and DFT), the experiments unravel the conformational preferences of HA upon aggregation to dimers and oligomers. The O-H···O═C intramolecular hydrogen bond present in the gas-phase monomer partially opens upon aggregation in supersonic expansions, giving rise to intermolecular cooperatively enhanced O-H···O-H hydrogen bonds in competition with isolated O-H···O═C hydrogen bonds. On the other hand, low-temperature IR studies on the neat solid and X-ray crystallographic data reveal that HA undergoes profound conformational changes upon crystallization, with the HOCC dihedral angle changing from ~0° in the gas phase to ~180° in the crystalline phase, hence giving rise to a completely new conformation. These conclusions are supported by theoretical calculations performed on the geometry derived from the crystalline phase.

Exploring cyclopentadienone antiaromaticity: charge density studies of various tetracyclones.

A systematic study of six tetracyclones has been carried out using experimental and theoretical charge density analysis. A three pronged approach based on quantum theory of atoms in molecules (QTAIM), nucleus independent chemical shifts (NICS) criterion, and source function (SF) contributions has been performed to establish the degree of antiaromaticity of the central five-membered ring in all the derivatives. Electrostatic potentials mapped on the isodensity surface show that electron withdrawing substituents turn both C and O atoms of the carbonyl group more electropositive while retaining the direction of polarity.

Vibrational and third-order nonlinear optical study on hydroxyethylammonium picrate (HEAP) single crystals

Single crystals of hydroxyethylammonium picrate (C8 H10N4O8; HEAP) have been grown for the first time by slow evaporation solution growth technique at room temperature, using ethanol as solvent. FT-IR and Raman spectra were recorded for HEAP at room temperature. The main vibrational bands related to NH3+ and CO− (picrate) groups, involved in charge transfer, are discussed. Second-order hyperpolarizability(γ) for the single crystal was evaluated theoretically to be 3.48×10−28 e.s.u. A Z-scan study of HEAP showed that the relative third-order nonlinear refractive index is −9.2×10−5cm2/W. The measured third-order nonlinear properties confirm the suitability of the crystal for optical limiting and switching applications.