Relativistic Frozen Density Embedding calculations of solvent effects on the NMR shielding constants of transition metal nuclei.

Nuclear Magnetic Resonance (NMR) shielding constants of transition metals in solvated complexes are computed at the relativistic density functional theory (DFT) level. The solvent effects evaluated with subsystem-DFT approaches are compared with the reference solvent shifts predicted from supermolecular calculations. Two subsystem-DFT approaches are analyzed – in the standard frozen density embedding (FDE) scheme the transition metal complexes are embedded in an environment of solvent molecules whose density is kept frozen, in the second approach the densities of the complex and of its environment are relaxed in the “freeze-and-thaw” procedure. The latter approach improves the description of the solvent effects in most cases, nevertheless the FDE deficiencies are rather large in some cases. Keywords — Frozen Density Embedding, NMR shielding constant, solvent shifts, transition-metal complexes

Critical analysis of spectral solvent shifts calculated by the contemporary PCM approaches of a representative series of charge-transfer complexes between tetracyanoethylene and methylated benzenes

The performance of different state-specific methods was compared with experiment and state-universal LR method.

A Simulation Study of the Fundamental Vibrational Shifts of HCl Diluted in Ar, Kr, and Xe: Anharmonic Corrections Effects

We have calculated the vibrational solvent shifts of the fundamental bands of HCl diluted in Ar, Kr, and Xe solutions at different thermodynamic conditions by means of the molecular dynamics technique and a model for the isotropic part of the interaction depending on the vibration. The theoretical vibrational shifts, which were compared with the available experimental data, have been determined by considering both, the usual linear Buckingham terms and the nonlinear anharmonic corrections, and the latter omitted in a previous work for the HCl in Ar and Kr. We have found that the Buckingham contributions dominate the solvent shifts of the fundamental bands of HCl in Ar, Kr, and Xe, although the anharmonic shifts’ present significant greater values than those obtained previously for N2 diluted in liquid Ar and pure liquid N2, both at normal conditions. We have analyzed the solvent shifts influence of the linear and quadratic (in the vibrational coordinate) oscillator-bath interaction terms and also the Dunham intramolecular potential effects on the anharmonic contributions.

ELECTRONIC EXCITATIONS OF GREEN FLUORESCENT PROTEINS: MODELING SOLVATOCHROMATIC SHIFTS OF CHROMOPHORE MODEL COMPOUNDS IN SOLUTIONS

Green fluorescent protein (GFP) is a spontaneously fluorescent protein due to its p-hydroxylbenzylideneimidazolidinone chromophore. In this work, we have investigated the electronic structures, liquid structures, and solvent shifts of the GFP chromophore model compounds 4′-hydroxylbenzylidene-2,3-dimethylimidazolin-5-one (HBDI) and 4′-hydroxylbenzylidene-2-methyl-imidazoin-5-one-3-acetate (HBMIA) in NaOH /aqueous solutions, in which both compounds are protonated at anionic state. The electronic structure calculations predict that both model compounds could adopt both cis and trans conformations in solutions. Moreover, liquid simulations elucidate an extensive well-defined hydrogen-bonding network between the solvent and the solute in the ground state. Furthermore, solvent shifts calculations indicate that contributions from the specific solute-solvent hydrogen-bonding interactions are negligible for the solvatochromatic shifts observed in the absorption spectrum of the model compounds in solutions; rather, the solvent shifts are dominated by the dipolar solvation in which both permanent charge–charge interactions and many-body polarizations contribute significantly. Self-Consistent Reaction-Field (SCRF) approach could be the efficient method for studying the unusual optical properties of the GFP chromophore in solutions and proteins.