Justin B. Ingels

Short Intramolecular Hydrogen Bonds : Derivatives of Malonaldehyde with Symmetrical Substituents

A systematic study of various derivatives of malonaldehyde has been carried out to explore very short hydrogen bonds (r(OO) < 2.450 A). Various electron-withdrawing groups, including CN, NO(2), and BH(2), have been attached to the central carbon atom, C(2). To C(1) and C(3), strong electron donors and/or sterically hindered substituents were used to strengthen the intramolecular hydrogen bond, including but not limited to NH(2), N(CH(3))(2), and C(CH(3))(3). Seven molecules (Figure 2 ) were found to have extremely short intramolecular hydrogen bonds. The chemical systems investigated are intriguing due to their low energetic barriers for the intramolecular hydrogen atom transfers. Classical barriers were predicted using correlated methods including second-order perturbation theory and coupled cluster theory in conjunction with the Dunning hierarchy of correlation consistent basis sets, cc-pVXZ (X = D, T, Q, 5). Focal point analyses allowed for the barriers to be evaluated at the CBS limit including core correlation and zero-point vibrational energy corrections. B3LYP energies are benchmarked against highly accurate correlated energies for intramolecular hydrogen bonded systems. The focal point extrapolated method, including coupled cluster full triple excitation contributions, gives a hydrogen transfer barrier for malonaldehyde of approximately 4 kcal mol(-1). We describe two compounds with extremely low classical barriers, nitromalonamide (0.43 kcal mol(-1)) and 2-borylmalonamide (0.60 kcal mol(-1)). An empirical relationship was drawn between the B3LYP energetic barriers and the predicted coupled cluster barriers at the CBS limit. By relating these two quantities, barrier heights may be estimated for systems too large to presently use highly correlated electronic structure methods.

Characterization of the HSiNHNSi system in its electronic ground state

The electronic ground states (X (1)Sigma(+)) of HSiN, HNSi, and the transition state connecting the two isomers were systematically studied using configuration interaction with single and double (CISD) excitations, coupled cluster with single and double (CCSD) excitations, CCSD with perturbative triple corrections [CCSD(T)], multireference complete active space self-consistent field (CASSCF), and internally contracted multireference configuration interaction (ICMRCI) methods. The correlation-consistent polarized valence (cc-pVXZ), augmented correlation-consistent polarized valence (aug-cc-pVXZ) (X=T,Q,5), correlation-consistent polarized core-valence (cc-pCVYZ), and augmented correlation-consistent polarized core-valence (aug-cc-pCVYZ) (Y=T,Q) basis sets were used. Via focal point analyses, we confirmed the HNSi isomer as the global minimum on the ground state HSiN_HNSi zero-point vibrational energy corrected surface and is predicted to lie 64.7 kcal mol(-1) (22 640 cm(-1), 2.81 eV) below the HSiN isomer. The barrier height for the forward isomerization reaction (HSiN-->HNSi) is predicted to be 9.7 kcal mol(-1), while the barrier height for the reverse process (HNSi-->HSiN) is determined to be 74.4 kcal mol(-1). The dipole moments of the HSiN and HNSi isomers are predicted to be 4.36 and 0.26 D, respectively. The theoretical vibrational isotopic shifts for the HSiN/DSiN and HNSi/DNSi isotopomers are in strong agreement with the available experimental values. The dissociation energy for HSiN [HSiN(X (1)Sigma(+))-->H((2)S)+SiN(X (2)Sigma(+))] is predicted to be D(0)=59.6 kcal mol(-1), whereas the dissociation energy for HNSi [HNSi(X (1)Sigma(+))-->H((2)S)+NSi(X (2)Sigma(+))] is predicted to be D(0)=125.0 kcal mol(-1) at the CCSD(T)/aug-cc-pCVQZ level of theory. Anharmonic vibrational frequencies computed using second order vibrational perturbation theory are in good agreement with available matrix isolation experimental data for both HSiN and HNSi isomers root mean squared derivation (RMSD=9 cm(-1)).

A Comparison of Willingness to Pay to Prevent Child Maltreatment Deaths in Ecuador and the United States

Estimating the benefits of preventing child maltreatment (CM) is essential for policy makers to determine whether there are significant returns on investment from interventions to prevent CM. The aim of this study was to estimate the benefits of preventing CM deaths in an Ecuadorian population, and to compare the results to a similar study in a US population. The study used the contingent valuation method to elicit respondents’ willingness to pay (WTP) for a 1 in 100,000 reduction in the risk of CM mortality. After adjusting for differences in purchasing power, the WTP to prevent the CM mortality risk reduction in the Ecuador population was

Linking Costs to Health Outcomes for Allocating Scarce Public Health Resources

237 and the WTP for the same risk reduction in the US population was

Cost-effectiveness of Legacy for ChildrenTM for Reducing BehavioralProblems and Risk for ADHD among Children Living in Poverty

175. In the pooled analysis, WTP for a reduction in CM mortality was significantly impacted by country (p = 0.03), history of CM (p = 0.007), payment mechanism (p < 0.001), confidence in response (p = 0.014), and appropriateness of the payment mechanism (p < 0.001). These findings suggest that estimating benefits from one culture may not be transferable to another, and that low- and middle-income countries, such as Ecuador, may be better served by developing their own benefits estimates for use in future benefit-cost analyses of interventions designed to prevent CM.

A Prospective Programmatic Cost Analysis of Fuel Your Life: A Worksite Translation of Dpp

Introduction: Resources for public health (PH) are scarce and policymakers face tough decisions in determining their funding priorities. The difficulty of making these decisions is compounded by current PH accounting systems, which are ill-equipped to link fiscal resources to PH outcomes. This paper examines the types of revenues and expenditures, health services, and health outcomes that are being tracked at the local and state PH levels. The authors provide recommendations for strengthening the ability of local and state governments to link expenditures to PH outcomes, both within and across jurisdictions. Framework and Next Steps: The source of revenue data for most local jurisdictions is the accounting systems used for the budgeting and auditing of fiscal activities, and these are primarily linked to specific PH programs. In contrast, expenditure data are mostly generic and typically span multiple PH programs with no link to specific PH activities. Many challenges exist to then link PH activities to health outcomes data, which are often collected through separate reporting systems at the local, state, and national levels. Policy change at the state level and implementation strategies that are standardized across local health departments are required to assess the costs and health outcomes of PH activities. Conclusion: Information linking PH expenditures to health outcomes of PH services could greatly inform the decision-making process. This information will allow investments in PH to be better understood and will provide a strong foundation for the PH services and systems research community to understand variation and drive improvement. Ultimately, these data could be used to improve accountability at the local and state PH department levels.

How much are Ecuadorians Willing to Pay to Reduce Maternal Mortality? Results from a Pilot Study on Contingent Valuation.

This paper describes the programmatic costs required for implementation of the Legacy for Children™ (Legacy) program at two sites (Miami and Los Angeles) and enumerate the cost-effectiveness of the program. Legacy provided group-based parenting intervention for mothers and children living in poverty. This cost-effectiveness analysis included two behavioral outcomes, behavioral problems, and attention-deficit/hyperactivity disorder (ADHD), and programmatic costs collected prospectively (2008 US

Race and Socioeconomic Status: Public Perceptions toward Quality and Access to Care in the Affordable Care Act

). Incremental costs, effects, the incremental cost-effectiveness ratio (ICER), and cost-effectiveness acceptability curves were estimated for the intervention groups relative to a comparison group with a 5 year analytic horizon. The intervention costs per family for Miami and Los Angeles were

Marginal Cost Analysis of Two Train-the-Trainer Models for Implementing SafeCare

16,900 and

Characterization of singlet ground and low-lying electronic excited states of phosphaethyne and isophosphaethyne

14,100, respectively. For behavioral problems, the incremental effects were marginally significant (p=0.11) for Miami with an ICER of