𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Ab initio molecular orbital calculations of the mechanism of oxidation of boron and aluminum monohalides

✍ Scribed by Wei Chen; H. Bernhard Schlegel

Publisher
Elsevier Science
Year
1995
Tongue
English
Weight
375 KB
Volume
241
Category
Article
ISSN
0009-2614

No coin nor oath required. For personal study only.

✦ Synopsis

The mechanisms of BF, BCI, AIF and AICI reacting with 302 have been investigated by ab initio molecular orbital methods at the PMP4/6-31G * and G2 levels of theory. The BX + 302 reactions proceed via an XBOO intermediate that can dissociate to give XBO + 30, which can react further to yield BO 2 + X. At the G2 level of theory, the initial barrier for BCI +302 is 8.5 kcal/mol and for BF +302 is 12.4 kcal/mol. These compare very favorably with the experimental barriers of 6.5 and 12 kcal/mol, obtained by fitting model transition states to the observed rate data. For AIX + 302, the barrier for XA1OO ~ XA10 +30 is much higher than the barrier for decomposition back to reactants, and the reaction may proceed by a different mechanism.

πŸ“œ SIMILAR VOLUMES

Ab initio molecular orbital calculations
Ab initio molecular orbital calculations of the static polarizabilities of xanthone analogues
✍ Takushi Sugino; Nobuaki Kambe; Noboru Sonoda; Toru Sakaguchi; Koji Ohta πŸ“‚ Article πŸ“… 1996 πŸ› Elsevier Science 🌐 English βš– 454 KB

The static polarizabilities, or, of various xanthone analogues (1-19) were estimated by ab initio molecular orbital calculations using the coupled perturbed Hartree-Fock (CPHF) method. The influence of basis sets on the calculated values was examined in detail and the reliability of the ECP approach

On the validity of polarization and corr
On the validity of polarization and correlation additivity in ab initio molecular orbital calculations
✍ Michael J. S. Dewar; Andrew J. Holder πŸ“‚ Article πŸ“… 1990 πŸ› John Wiley and Sons 🌐 English βš– 301 KB

A common approximation used in ab initio molecular orbital calculations assumes that the changes in energy due to use of a larger basis set (as in the inclusion of polarization orbitals) and to allowance for electron correlation are additives. Thus, small basis sets may be used for correlated ab ini