Atomization enthalpies, computational

The electronic energy calculated by the MINDO/3, MNDO, AMI, and PM3 methods is normally converted automatically in the computer program (Table 2) to an enthalpy of formation by subtracting the electronic energy of the isolated atoms and adding the experimental atomic enthalpies of formation. The zero-point energies and temperature corrections (0 to 298 K) are assumed to be included implicitly by the parameterization. For a molecule ABH, the AHf is defined in these methods as... 

The force field for ethanol [252] consists of three LJ 12-6 sites plus three point charges and was parameterized to ab initio and experimental data. The nucleus positions of aU ethanol atoms were computed by QM at the HF level of theory with a 6-3IG basis set. This force field is also based on the anisotropic approach of Ungerer et al. [130]. The LJ parameters and the anisotropic offset were fitted to experimental saturated liquid density, vapor pressure, and enthalpy of vaporization. The simulation results from this ethanol force field deviate on average from experimental values of vapor pressure, saturated liquid density, and heat of vaporization by 3.7, 0.3, and 0.9%, respectively. 

After you choose the computation method and options, you can use Start Log on the File menu to record results, such as total energies, orbital energies, dipole moments, atomic charges, enthalpies of formation (for the CNDO, INDO, MINDO/3, MNDO, AMI, PM3, ZINDO/I, and ZINDO/S methods), etc. 

Compute the enthalpy change for the destruction of ozone by atomic chlorine by subtracting the dissociation energies of O2 and CIO from the dissociation energy for ozone. What model chemistry is required for accurate modeling of each phase of this process The experimental values are given below (in kcal-moT ) ... 

Molecular mechanics (also known diS force-field calculations) is a method for the calculation of conformational geometries. It is used to calculate bond angles and distances, as well as total potential energies, for each conformation of a molecule. Steric enthalpy can be calculated as well. Molecular orbital calculations (p. 34) can also give such information, but molecular mechanics is generally easier, cheaper (requires less computer time), and/or more accurate. In MO calculations, positions of the nuclei of the atoms are assumed, and the wave equations take account only of... 

As shown in Table 3, triplet lb is computed to be 25-26 kcal/mol lower in enthalpy than triplet lc.77 Table 3 also shows that radicals 8b and 8c, formed by adding a hydrogen atom to lb and lc, respectively, differ in enthalpy by only 1-3 kcal/mol. Therefore, the large enthalpy difference between 3lb and 3lc is not due to a difference between the abilities of the phenyl and pyridyl groups to stabilize an unpaired tt electron. Instead it must reflect an intrinsic enthalpy difference between arylnitrenes and arylcarbenes. Table 3 also shows that aniline (9b) and fl-picoline (9c) are also predicted to have very similar enthalpies, thus providing further evidence that the large enthalpy difference between lb and lc is, indeed, due to the fact that lb is a nitrene, while lc is a carbene. 

Equation (1.11) is now examined closely. If the s (products) total a number / , one needs (// + 1) equations to solve for the // n s and A. The energy equation is available as one equation. Furthermore, one has a mass balance equation for each atom in the system. If there are a atoms, then (/t - a) additional equations are required to solve the problem. These (// a) equations come from the equilibrium equations, which are basically nonlinear. For the C—H—O—N system one must simultaneously solve live linear equations and (/t - 4) nonlinear equations in which one of the unknowns, T2, is not even present explicitly. Rather, it is present in terms of the enthalpies of the products. This set of equations is a difficult one to solve and can be done only with modem computational codes. 

All computed and experimental values are from NIST Computational Chemistry Comparison and Benchmark Database, NIST Standard Reference Database No. 101, Release 12 (Ed. R. D. Johnson III), 2005. htti) //srdata.nistgov/cccbdb Energy minimum at 0 K 1 hartree = 627.5 kcalmoLL Enthalpy required to separate molecule into atoms at 298 K. 

This book is about electronic charge distributions, chemical bonds, bond energy additivity in organic molecules, and the description of their relevant thermochemical properties, such as the energy of atomization, the enthalpy of formation, and the like, using computer-friendly methods. 

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