Digitale Medien
College Park, Md.
:
American Institute of Physics (AIP)
The Journal of Chemical Physics
110 (1999), S. 3765-3768
ISSN:
1089-7690
Quelle:
AIP Digital Archive
Thema:
Physik
,
Chemie und Pharmazie
Notizen:
Ab initio calculations of the HBO+→BOH+potential energy surface were performed at the QCISD(T)/6−311++G(2df,2pd) level of theory. A linear 2Σ+ +B=O-H species was found to be the global minimum for the cation although the linear 1Σ+ H-B(Triple Bond)O isomer is the global minimum on the neutral HBO→BOH surface. Which isomer of the cation appears in various experimental circumstances depends on how the cation is produced. Ionization of 1Σ+ HBO should occur near 13.2 eV and will produce the metastable linear H-B(Double Bond)O+(2Π) π-radical cation, which is 36.9 kcal/mol higher in energy than 2Σ+ +B(Double Bond)O-H and is separated from +B(Double Bond)O-H by a 36.3 kcal/mol classical barrier. Ionization of HBO with less than 37 kcal/mol of excess energy will thus yield 2Π H-B(Double Bond)O+; if the excess energy exceeds 37 kcal/mol, rearrangement to the 2Σ++B(Double Bond)O-H σ-radical cation can occur. Production of the cation via exothermic chemical reaction will likely give the more stable 2Σ+ +B(Double Bond)O-H isomer. The stability of the 2Σ+ +B(Double Bond)O-H cation relative to 2Π H-B(Double Bond)O+ is due primarily to the large difference in the energies required to remove an electron from a π bonding orbital in H-B(Triple Bond)O or from a nonbonding boron-localized σ orbital in BOH. © 1999 American Institute of Physics.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1063/1.478266
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