Complete report - Donostia International Physics Center - Euskal ...

www.rsc.org/pccp Volume 12 | Number 40 | 28 October 2010 | Pages 12877–13344
ISSN 1463-9076
COVER ARTICLE
Lopez et al.
Performance of PNOF3 for
reactivity studies: X[BO] and X[CN]
isomerization reactions as a case
study
PERSPECTIVE
Wittstock et al.
Nanoporous gold: a new material for
catalytic and sensor applications
1463-9076(2010)12:40;1-Y
2010 DIPC Highlight
Performance of PNOF3 for
reactivity studies: X[BO] and X[CN]
isomerization reactions (X H, Li)
as a case study
X. Lopez, M. Piris, J.M. Matxain and J.M. Ugalde
Physical Chemistry Chemical Physics 12, 12931-12934 (2010)
Natural Orbital Functional Theory in its PNOF3 implementation is
used to investigate the potential energy surfaces of four isomerization
reactions: (i) BOH to HBO; (ii) BOLi to LiBO; (iii) CNH to HCN;
and (iv) CNLi to LiCN. These reactions are taken as a case study to
illustrate the potentiality of PNOF3 to yield the correct topology
for reactions sensible to electron correlation. The perfomance of
PNOF3 to yield accurate reaction barriers and isomerization energies
is also discussed. We have found that PNOF3 shows promising
behaviour in the description of these delicate PESs, and yield the
correct trends in isomerization energies and reaction barriers,
although the latter trends tend to be somewhat lower than the
ones calculated at highly correlated levels of theory. The present
results show that PNOF3 can give a balanced description of electron
correlation in both equilibrium and non-equilibrium structures.
Physical Chemistry Chemical Physics
Natural Orbital Functional Theory in its PNOF3 implementation is able to
describe reactions with outstanding chemical accuracy in equilibrium and
non-equilibrium structures that are highly sensible to electron correlation.
Potential Energy Surfaces as a function of the XBO and XCN (X=H,Li) angle. Results obtained from single-point
PNOF3 and CCSD(T,Full) energies at the CCSD partially optimized geometries with XBO/XCN angle frozen at
values that range from 0 o to 180 o with 10 o variation. All calculations were done with the cc-pVTZ basis set. The
relative energies, in kcal/mol, are calculated with respect to the energy of the 0 o structure. Notice the good perfomance
of PNOF3 in describing the topology of the four PES’s.
36 DIPC 10/11
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