1 research outputs found
Calculating the NMR Chemical Shielding of Large Molecules
This thesis examines three approximations that significantly
reduce the computational time of theoretical NMR shielding
calculations for large molecules, whilst largely retaining the
accuracy of the parent method: fragmentation, locally dense basis
sets and composite methods.
For fragmentation it is established that Level 4 fragments
reliably reproduce full molecule shieldings, when hydrogen bonds
are treated as single bonds, and long range through space
corrections are incorporated through the McConnell equation and
background charges.
The pcS-n basis set family is demonstrated to converge more
rapidly towards the basis set limit than all other examined
families. Furthermore, it is established that this limit is
consistent with convergence towards experimental values.
A systematic investigation of locally dense basis sets
established that a group based partitioning of the pcS-4, pcS-2
and pcS-1 basis sets, augmented with through space allocations,
allowed the shielding to be produced within chemical accuracy for
a variety of compounds.
Finally, composite methods utilising a variety of levels of
theory were systematically investigated, and it was found that a
double composite method combining the HF, MP2 and CCSD(T) levels
of theory and the pcS-4, pcS-2 and pcS-1 basis sets yielded NMR
shieldings that were within chemical accuracy of CCSD(T)/pcS-4
calculations, themselves having converged closely to experimental
values.
When considered in combination this work represents a significant
step towards achieving chemical accuracy for protein NMR
shielding calculations