RT info:eu-repo/semantics/article
T1 The equilibrium molecular structures of 2-deoxyribose and fructose by the semiexperimental mixed estimation method and coupled-cluster computations
A1 Vogt, Natalja
A1 Demaison, Jean
A1 Cocinero, Emilio José
A1 Écija, Patricia
A1 Lesarri Gómez, Alberto Eugenio
A1 Rudolph, Heinz Dieter
A1 Vogt, Jurgen
AB ructose and deoxyribose (24 and 19 atoms, respectively) are too large for determining accurateequilibrium structures, either by high-level ab initio methods or by experiments alone. We show in thiswork that the semiexperimental (SE) mixed estimation (ME) method offers a valuable alternative forequilibrium structure determinations in moderate-sized molecules such as these monosaccharides orother biochemical building blocks. The SE/ME method proceeds by fitting experimental rotational datafor a number of isotopologues, which have been corrected with theoretical vibration–rotation inter-action parameters (ai), and predicate observations for the structure. The derived SE constants are latersupplemented by carefully chosen structural parameters from medium level ab initio calculations,including those for hydrogen atoms. The combined data are then used in a weighted least-squares fit todetermine an equilibrium structure (rSE). We applied the ME method here to fructose and 2-deoxyribose eand checked the accuracy of the calculations for 2-deoxyribose against the high level ab initio rBO structure efully optimized at the CCSD(T) level. We show that the ME method allows determining a complete and reliable equilibrium structure for relatively large molecules, even when experimental rotational information includes a limited number of isotopologues. With a moderate computational cost the ME method could be applied to larger molecules, thereby improving the structural evidence for subtle orbital interactions such as the anomeric effect.
PB RSC
YR 2016
FD 2016
LK http://uvadoc.uva.es/handle/10324/25471
UL http://uvadoc.uva.es/handle/10324/25471
LA eng
NO Physical Chemistry Chemical Physics, 2016, 18, 15555
NO Producción Científica
DS UVaDOC
RD 24-nov-2024