Hydrogen energy decomposition analysis

Glendening, E. D., Streitwieser, A., 1994, Natural Energy Decomposition Analysis An Energy Partitioning Procedure for Molecular Interactions With Apphcation to Weak Hydrogen Bonding, Strong Ionic, and Moderate Donor-Acceptor Interactions , J. Chem. Phys., 100, 2900. 

In order to obtain more information on the solvation process Yang and Cui performed a so called natural energy decomposition analysis (NEDA) on monomethyl phosphate ester (MMP) solvated in water. They used a supermolecular approach where the solute plus a number of water molecules (up to 34) were treated quantum-mechanically. A further set of water molecules was treated with a force-field model. Their results indicate that there is a substantial charge transfer between the solute and the nearest solvent molecules. The interaction energy due to this transfer was found to amount to some 70-80% of that of the electric interactions. Since MMP forms hydrogen bonds with the water molecules, all results together suggests that for such a system it is important to include the nearest solvent molecules in the quantum-mechanical treatment, whereas a continuum approximation or a force field may not be sufficiently accurate. 

Table 4 Interaction energies of CWO hydrogen bonds (Morokuma energy decomposition analysis)...

Figure 4.1 Illustration of the density based energy decomposition analysis (DEDA) scheme. Reprinted with permission from Lu, Z., Zhou, N., Wu, Q. and Zhang, Y. Directional dependence of hydrogen bonds A density-based energy decomposition analysis and its implications on force field development. J Chem Theory Comput 7, 4038-4049 (2011). Copyright (2011) American Chemical Society.

Glendening, E. D., and Streitwieser, A. [1994], Natural energy decomposition analysis An energy partitioning procedure for molecular Interactions with application to weak hydrogen bonding strong ionic, and moderate donor-acceptor interactions,/ Chem. Phys. 100, pp. 2900-2909. 

Rosen, M. A. (2008). Exergy analysis of hydrogen production by thermochemical water decomposition using the Ispra Mark-10 Cycle. International Journal of Hydrogen Energy, 33, 6921-6933. 

The first and very popular energy decomposition scheme that is used to decompose the total INT into various contributing factors was developed by Kitaura and Moroknma in the late 1970s. This method was mainly developed to decompose the INT of hydrogen-bonded systans within the Hartree-Fock approximation. Since then, it has also been successfully applied to donor-acceptor pairs, % and a interactions in transition metal complex, and decomposition of electron density. A broad outline of the key steps involved in the analysis of various components of the INT is provided in the following section. Before we proceed to the KM analysis in detail, it is important to look at the initial decomposition scheme developed by Morokuma. We start the discussion by taking a dimer AB into consideration. 

As mentioned above, the method of KM is the most widely used variational energy decomposition method and works well for hydrogen-bonded systems, but it is not completely foolproof. Some of the shortcomings of the KM scheme include its limitation to only the HF method the final INT obtained is not corrected for unphysical lowering of energy caused by the basis set superposition error (BSSE). Also, molecular complexes separated by short distances, for instance, the cation-jt complexes of benzene with Li+ and Mg +, exhibit numerical instabilities in POL and CT energies. Several alternative schemes have been proposed to avoid problans of the KM EDA, one among which is the RVS analysis developed by Stevens and Fink and has been successfully applied to molecular complexes with various kinds of interactions. 

Huang, C., Raissi, T.-A. 2005. Analysis of sulfur-iodine thermochemical cycle for solar hydrogen production. Part I decomposition of sulfuric acid. Solar Energy 78 632-646. 

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