DFT and TD-DFT study of hydrogen bonded complexes of aspartic acid and n water (n = 1 and 2).

CONTEXT: Hydrogen bonds (HB) influence the conformational preferences of biomolecules and their optical and electronic properties. The directional interaction of molecules of water can be a prototype to understand the effects of HBs on biomolecules. Among the neurotransmitters (NT), L-aspartic acid (ASP) stands out due to its importance in health and as a precursor of several biomolecules. As it presents different functional groups and readily forms inter- and intramolecular HBs, ASP can be considered a prototype for understanding the behavior of NTs when interacting by HB with other substances. Although several theoretical studies have been performed in the past on isolated ASP and its formed complexes with water, both in gas and liquid phases, using DFT and TD-DFT formalisms, these works did not perform large basis set calculations or study electronic transitions of ASP-water complexes. We investigated the HB interactions in complexes of ASP and water molecules. The results show that the interactions between the carboxylic groups of ASP with water molecules, forming cyclic structures with two HBs, lead to more stable and less polar complexes than other conformers formed between water and the NH2 group. It was observed that there is a relationship between the deviation in the UV-Vis absorption band of the ASP and the interactions of water with the HOMO and LUMO orbitals with the stabilization/destabilization of the S1 state to the S0 of the complexes. However, in some cases, such as 1:1 complex ASP-W2, this analysis may be inaccurate due to small changes in ΔE. METHODS: We studied the landscapes of the ground state surface of different conformers of isolated L-ASP and the L-ASP-(H2O)n complexes (n = 1 and 2) using the DFT formalism, with the B3LYP functional, and six different basis sets: 6-31 + + G(d,p), 6-311 + + G(d,p), D95 + + (d,p), D95V + + (d,p), cc-pVDZ, and, cc-pVTZ basis sets. The cc-pVTZ basis set provides the minimum energy of all conformers, and therefore, we performed the analysis with this basis set. We evaluated the stabilization of the ASP and complexes using the minimum ground state energy, corrected by the zero point energy and the interaction energy between the ASP and the water molecules. We also calculated the vertical electronic transitions S1 ← S0, and their properties using the TD-DFT formalism at B3LYP/cc-pVTZ level with the optimized geometries for S0 state with the same basis set. For the analysis of the vertical transitions of isolated ASP and the ASP-(H2O)n complexes, we calculated the electrostatic energy in the S0 and S1 states. We performed the calculations with the Gaussian 09 software package. We used the VMD software package to visualize the geometries and shapes of the molecule and complexes.

Theoretical investigation of perylene dimers and excimers and their signatures in X-ray diffraction.

The structures of the ground and excimer states of perylene pairs are calculated [using density functional theory (DFT) and time-dependent DFT techniques] in a free as well as a crystal environment, and their spectroscopic properties are studied for the most stable configurations. The vertical transition energies for the absorption and emission bands are obtained, and they are in good agreement with experimental data. In these calculations, up to six excited states are considered. With the calculated structures of the ground and excimer states, the scattering factors are analyzed as a function of the concentration of excimers in a crystal. The intensity of the 110, 005, and 0 10 0 reflections are found to be fairly sensitive to the presence of excimers in the crystal. The finite (nanosecond) lifetime of the excimer may make it possible to observe this state using time-resolved X-ray diffraction techniques.