A theoretical examination of solvatochromism and solute-solvent structuring in simple alkyl carbonyl compounds. Simulations using statistical mechanical free energy perturbation methods

Electronic properties of formaldehyde in water: a theoretical study

“…3). To our knowledge the only other computational attempt to evaluate the excitation free energy of formaldehyde in water has been performed by DeBolt and Kollman [33]. In that Letter, the authors provide the excitation free energy at 298 K together with the average excitation energy shift, not equivalent to the shift of the thermodynamic energy (excitation internal energy), both neglecting any vibrational effects.…”

X-ray and molecular dynamics study of liquid structure in pure methylchloromethane compounds ((CH3)4−nCCln)

“…Although there is a basic coincidence regarding its Lennard-Jones parameters, a noticeable dispersion exists regarding electrostatic interactions. In most cases, they have been neglected altogether, [16][17][18] a reasonable choice given the nonpolar nature of the isolated molecule; however, some workers have also used fixed partial charges, 16,19,20 with a considerable dispersion in values ͑the charge on the Cl center spans the range 0.35͉e͉ to Ϫ1.2͉e͉); 20 and finally, even polarizable models have been studied. 21,22 The choices for the partial charges, when different from zero, range from purely phenomenological determinations 16,20 to ab initio methods.…”

“…21,22 The choices for the partial charges, when different from zero, range from purely phenomenological determinations 16,20 to ab initio methods. 19,21,22 In the opposite extreme of the series, neopentane does not present such a dispersion, in all cases the united atom approximation has been used for the methyl group and electrostatic forces neglected, 23,24 although the functional description of short range interactions differs somewhat. Finally, a simple molecular model also exists for tert-butyl chloride 25 which adopts the pseudoatom approach for the methyls, but assigns partial charges only to the chlorine and carbon centers.…”

The specific and nonspecific solvatochromic behavior of Sudan dyes in different solvents

“…Aside from substituent change, it is known that the photo-physical behavior of a dissolved substance is strongly influenced by its environment [17][18][19].…”