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.

Invariant barriers to reactive front propagation in fluid flows

We present theory and experiments on the dynamics of reaction fronts in two-dimensional, vortex-dominated flows, for both time-independent and periodically driven cases. We find that the front propagation process is controlled by one-sided barriers that are either fixed in the laboratory frame (time-independent flows) or oscillate periodically (periodically driven flows). We call these barriers burning invariant manifolds (BIMs), since their role in front propagation is analogous to that of invariant manifolds in the transport and mixing of passive impurities under advection. Theoretically, the BIMs emerge from a dynamical systems approach when the advection-reaction-diffusion dynamics is recast as an ODE for front element dynamics. Experimentally, we measure the location of BIMs for several laboratory flows and confirm their role as barriers to front propagation.

Barriers to front propagation in ordered and disordered vortex flows

We present experiments on reactive front propagation in a two-dimensional (2D) vortex chain flow (both time-independent and time-periodic) and a 2D spatially disordered (time-independent) vortex-dominated flow. The flows are generated using magnetohydrodynamic forcing techniques, and the fronts are produced using the excitable, ferroin-catalyzed Belousov-Zhabotinsky chemical reaction. In both of these flows, front propagation is dominated by the presence of burning invariant manifolds (BIMs) that act as barriers, similar to invariant manifolds that dominate the transport of passive impurities. Convergence of the fronts onto these BIMs is shown experimentally for all of the flows studied. The BIMs are also shown to collapse onto the invariant manifolds for passive transport in the limit of large flow velocities. For the disordered flow, the measured BIMs are compared to those predicted using a measured velocity field and a three-dimensional set of ordinary differential equations that describe the dynamics of front propagation in advection-reaction-diffusion systems.

Wom(b)anism: Reading Relationships Between the Community and the Womb in Sankofa, The Women of Brewster Place, and Corregidora

This project attempts to contribute to the various discourses within the black womanist tradition. In 1983, Alice Walker published her landmark collection of essays entitled In Search of Our Mother Gardens: Womanist Prose. At the outset of the volume, Walker defines the core concept of womanism. After a poetic four-part definition of the term womanist, Walker concludes by stating, 'womanist is to feminist as purple to lavender' (Phillips 19). Although this analogy is critically engaged, the scholarly discourse that emerged in response to Walker's proposition shapes the intellectual inner workings of this project. Certain established concepts (such as ancestral mediation or the laying on of hands) work in conjunction with my own concepts of 'wom(b)anism' and 'the communal womb' to frame the interpretive discussions throughout these pages. Wom(b)anism and the communal womb both emerge from the black feminist and womanist traditions, especially via the role of ancestral mediation but also within the contested discourses on womanism itself. I apply the two concepts (wom(b)anism and the communal womb) to my readings of Haile Gerima's Sankofa, Gloria Naylor's The Women of Brewster Place, and Gayl Jones' Corregidora. The relationship between the community and women's wombs across each of these texts construct a narrative that features ancestral mediation (or intervention), various acts of violence committed against women's bodies, and the complicated circumstances through which women heal themselves andtheir communities.

Testing the TICT State Hypothesis: an Investigation into the Solvatochromic Behavior of 2-Naphthalenylmethylene Malononitrile

Towards the goal of investigating the possible Twisted Intramolecular Charge Transfer (TICT) state mechanism of fluorescence emission, two aromatic dicyanovinyl compounds, 2-(naphthalene-2-ylmethylene) malononitrile (DCN) and a rigidified analogue, 3,4-dihydrophenanthren-1(2H)-ylidene)malononitrile (RDCN) were synthesized and their absorption and steady-state fluorescence emission spectra characterized. The spectral characterization was divided into two studies: first, DCN and RDCN were characterized in liquid solvents of increasing polarity; second, DCN and RDCN were characterized in viscous solvents and rigid glass media. The absorption spectra for both DCN and RDCN in all solvents demonstrated little to no solvatochromism. Emission results for DCN and RDCN in liquid solvents of increasing polarity showed DCN possessing strong solvatochromism while RDCN showed much less solvatochromism. Using the Lippert-Mataga equation, the difference between the ground and excited state dipole moment for DCN was estimated to be 8.4 + 0.4 Debye and between ~3.0 to 5.0 Debye for RDCN. Quantum yield measurements for DCN and RDCN in hexane, diethyl ether and acetonitrile were less than 0.01 and independent of polarity for both both solvents, with DCN generally possessing a quantum yield 3-4 times greater than RDCN. Experiments in glass media for DCN and RDCN showed a lessening of their solvatochromic character in both polar and non-polar glasses. These data provide strong evidence for a link between molecular flexibility and solvatochromism. However, while these data are consistent with a TICT state hypothesis for the emission mechanism, an alternative mechanism proposed by Maroncelli et al.10 involving rotation about the dicyanovinyl double bond in the excited state remains a possibility as well.