DOI: 10.1039/C5RA00374A
RSC Advances
ARTICLE
Journal Name
The samples were withdrawn periodically and analyzed on structures reported in the manuscript. The contributions of
Agilent 6890 Gas chromatograph equipped with a HP-5 internal energy and entropy were further obtained from
dimethyl polysioxane column (60 m length, 0.25 mm diameter frequency calculations done on the DFT structures at 298.15 K.
and 0.25 µm film thicknesses with flame ionization detector. Thus, the energies reported in the figures of the paper are the
Products were confirmed by injecting the authentic on GC and ΔG values. Solvent effects were incorporated using the
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also GC-MS.
COSMO model , with acetonitrile (ε = 37.5). Solvent effects
were incorporated in the following fashion: single point
calculations were done, with COSMO included, on all the
structures that had been obtained from the gas phase
Computational Details
The computational procedure adopted is as follows: all the calculations. The frequency calculations were done on the gas
structures reported in the manuscript have been optimized using phase optimized structures, and the contribution of the entropy
density functional theory (DFT) with the Turbomole suite of and zero point energy was included from the frequency
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5
programs, using Turbomole Version 6.4. The geometry calculations. The comparison of the
H and
G values in the
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optimizations were performed using the BP-86 functional.
gas phase and with COSMO included is shown in (Table ST-3)
The electronic configuration of the atoms was described by a of the supporting information file. The actual optimized images
triple-zeta basis set augmented by a polarization function of all the all the reactants, intermediates and transition states are
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(
TURBOMOLE basis set TZVP). Since it is possible that the given in ESI S-16 and 17†.
geometry optimization procedure with DFT may be sensitive to
the nature of the functional, all the structures were also Acknowledgements
optimized with the Perdew, Burke, and Erzenhof density
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33, 34
functional (PBE), as well as with the B3LYP functional,
AVB acknowledges Director CSIR-NCL for providing QHS
and the TZVP basis set, in order to make sure that the results and in-house project MLP 028026 and SERB (DST) Government
did not vary significantly with the change of the functional. The of India for fast-track project no SERB/F/6598/2013-14.
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5
resolution of identity (RI),
along with the multipole
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accelerated resolution of identity (marij) approximations were
employed for an accurate and efficient treatment of the
electronic Coulomb term for both of the sets of the density
functional calculations. A comparison was then done between
the corresponding structures obtained with the BP-86 and the
PBE and B3LYP functionals. The comparison showed very
little difference in bond lengths, angles and dihedral values
between the corresponding structures for all the cases (ESI S8-
References
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1
,
[
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, 102, 3589-3614.
,
,
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5†). A further corroboration of the smallness of the difference
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, 26, 62-69.
between the structures obtained from the two functional came
from the comparison of the potential energy surfaces for the
different reactions discussed in the manuscript. The ΔE values
for the insertion and termination barriers for the epoxidation
mechanism, obtained from the three separate set of calculations,
were compared and the results, shown in the supporting
information, indicate that there is only slight difference
between the corresponding values for almost all the cases for
the energies obtained with the BP-86 and the PBE functionals.
The energies obtained from the B3LYP functionals were found
to be different by 8-10 kcal/mol from the corresponding BP-86
and PBE values. This suggests that changing the functional may
result in a change of the absolute values of the barriers in the
different mechanisms, but that the essential conclusions reached
in the manuscript will remain unchanged. With regard to the
transition states obtained from the three sets of calculations,
care was taken to ensure that the obtained transition state
structures possessed only one imaginary frequency
corresponding to the correct normal mode. No other imaginary
frequencies were present. Table ST3† in the supporting
information file shows the values of the imaginary frequencies
that have been obtained for the different transition state
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| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012