Molecular thermochemistry

The applications of isoperibol titration calorimetry to molecular thermochemistry studies are numerous and diverse [194,207], A few examples are presented next. 

The prospects of DSC, have been reviewed in a special issue of Thermochimica Acta, which includes a collection of articles on advances of thermal analysis in the twentieth century and expected future developments [232,235,236]. This journal and the Journal of Thermal Analysis and Calorimetry, where research articles about DSC and its applications are often published, are very useful sources of information on the technique. Although relatively old, the reviews by McNaughton and Mortimer [237] and by Mortimer [238] contain excellent examples of applications of DSC to molecular thermochemistry studies. The analytical uses of DSC, which are outside the scope of this book, can be surveyed, for example, in biannual reviews that appear in the journal Analytical Chemistry [239],... 

The determination of the heat capacity of a substance as a function of the temperature is by itself a very important application of DSC, because it may lead to values of the thermodynamic functions S%, //-" — //q, and Gy, mentioned in chapter 2. An example is the study of C6o carried out by Wunderlich and co-workers [271], The application of DSC in the area of molecular thermochemistry has been particularly important to investigate trends in transition metal-ligand bond dissociation enthalpies. The typical approach used in these studies, and its limitations, can be illustrated through the analysis of the reaction 12.27, carried out by Mortimer and co-workers [272] ... 

Quantum Chemistry Methods for the Prediction of Molecular Thermochemistry... 

Kruse, H. Goerigk, L. Grimme, S. Why the standard B3LYP/6-31G model chemistry should not be used in DFT calculations of molecular thermochemistry understanding and correcting the problem, 7. Org. Chem. 2012, 77, 10824-10834. 

Many of the technical issues involved in computer-aided model-construction have previously been reviewed by Tomlin et al. (1997). Several researchers, most notably Bozzelli, have extended Benson s method for estimating molecular thermochemistry using quantum chemistry (Lay and Bozzelli, 1997a, b Lay et al., 1995). Sumathi and Green (2002) have discussed how quantum chemistry can supplement experiments in developing rate estimation. Matheu et al. have shown how to automate the computation of rates of chemically-activated (pressure-dependent) reactions (Matheu, 2003 Matheu et al., 2003a, b). Here we focus on a few issues which have not been so thoroughly discussed in the literature ... 

There are several computational approaches for predicting gas-phase, molecular thermochemistry. For common organic compounds, empirical... 

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