Comparison of Model Chemistry and Density Functional Theory Thermochemical Predictions with Experiment for Formation of Ionic Clusters of the Ammonium Cation Complexed with Water and Ammonia; Atmospheric Implications

The G2, G3, CBS-QB3, and CBS-APNO model chemistry methods and the B3LYP, B3P86, mPW1PW, and PBE1PBE density functional theory (DFT) methods have been used to calculate ΔH° and ΔG° values for ionic clusters of the ammonium ion complexed with water and ammonia. Results for the clusters NH4+(NH3)n and NH4+(H2O)n, where n = 1−4, are reported in this paper and compared against experimental values. Agreement with the experimental values for ΔH° and ΔG° for formation of NH4+(NH3)n clusters is excellent. Comparison between experiment and theory for formation of the NH4+(H2O)n clusters is quite good considering the uncertainty in the experimental values. The four DFT methods yield excellent agreement with experiment and the model chemistry methods when the aug-cc-pVTZ basis set is used for energetic calculations and the 6-31G* basis set is used for geometries and frequencies. On the basis of these results, we predict that all ions in the lower troposphere will be saturated with at least one complete first hydration shell of water molecules.

Comparison of CBS-QB3, CBS-APNO, G2, and G3 thermochemical predictions with experiment for formation of ionic clusters of hydronium and hydroxide ions complexed with water

The GAUSSIAN 2, GAUSSIAN 3, complete basis set-QB3, and complete basis set-APNO methods have been used to calculate ΔH∘ and ΔG∘ values for ionic clusters of hydronium and hydroxide ions complexed with water. Results for the clusters H3O+(H2O)n andOH−(H2O)n, where n=1–4 are reported in this paper, and compared against experimental values contained in the National Institutes of Standards and Technology (NIST) database. Agreement with experiment is excellent for the three ab initio methods for formation of these clusters. The high accuracy of these methods makes them reliable for calculating energetics for the formation of ionic clusters containing water. In addition this allows them to serve as a valuable check on the accuracy of experimental data reported in the NIST database, and makes them useful tools for addressing unresolved issues in atmospheric chemistry.

Effective Length K-Factors For Flexural Buckling Strengths Of Web Members In Open Web Steel Joists

Open web steel joists are designed in the United States following the governing specification published by the Steel Joist Institute. For compression members in joists, this specification employs an effective length factor, or K-factor, in confirming their adequacy. In most cases, these K-factors have been conservatively assumed equal to 1.0 for compression web members, regardless of the fact that intuition and limited experimental work indicate that smaller values could be justified. Given that smaller K-factors could result in more economical designs without a loss in safety, the research presented in this thesis aims to suggest procedures for obtaining more rational values. Three different methods for computing in-plane and out-of-plane K-factors are investigated, including (1) a hand calculation method based on the use of alignment charts, (2) computational critical load (eigenvalue) analyses using uniformly distributed loads, and (3) computational analyses using a compressive strain approach. The latter method is novel and allows for computing the individual buckling load of a specific member within a system, such as a joist. Four different joist configurations are investigated, including an 18K3, 28K10, and two variations of a 32LH06. Based on these methods and the very limited number of joists studied, it appears promising that in-plane and out-of-plane K-factors of 0.75 and 0.85, respectively, could be used in computing the flexural buckling strength of web members in routine steel joist design. Recommendations for future work, which include systematically investigating a wider range of joist configurations and connection restraint, are provided.