Accurate relative pKa calculations for carboxylic acids using complete basis set and Gaussian-n models combined with continuum solvation methods

The complete basis set methods CBS-4, CBS-QB3, and CBS-APNO, and the Gaussian methods G2 and G3 were used to calculate the gas phase energy differences between six different carboxylic acids and their respective anions. Two different continuum methods, SM5.42R and CPCM, were used to calculate the free energy differences of solvation for the acids and their anions. Relative pKa values were calculated for each acid using one of the acids as a reference point. The CBS-QB3 and CBS-APNO gas phase calculations, combined with the CPCM/HF/6-31+G(d)//HF/6-31G(d) or CPCM/HF/6-31+G(d)//HF/6-31+G(d) continuum solvation calculations on the lowest energy gas phase conformer, and with the conformationally averaged values, give results accurate to ½ pKa unit. © 2001 American Institute of Physics.

Fantasy Making the Invisible Visible: Liminality in Neil Gaiman's Neverwhere and American Gods

The purpose of this thesis was to examine the ways in which the fantasy genre is ideally positioned for discussing social issues, such as invisibility and liminality. Elements associated with invisibility, such as poverty, homelessness, and alienation, were explored within two novels by Neil Gaiman: Neverwhere and American Gods. Gaiman's application of these elements within the fantasy genre were juxtaposed with samples from other genres, including Plato's 'Parable of the Cave' and Jennifer Toth's The Mole People. Another aim was to contrast Gaiman's use of the 'beast in the sewer' metaphor with previous renditions of the myth, demonstrating how fantasy, paradoxically, offers a unique and privileged view of reality.