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Title: The equilibrium molecular structures of 2-deoxyribose and fructose by the semiexperimental mixed estimation method and coupled-cluster computations
Authors: Vogt, Natalja
Demaison, Jean
Cocinero, Emilio J.
Écija, Patricia
Lesarri, Alberto
Rudolph, Heinz-D.
Vogt, Jurgen
Issue Date: 2016
Publisher: RSC
Description: Producción Científica
Citation: Physical Chemistry Chemical Physics, 2016, 18, 15555
Abstract: ructose and deoxyribose (24 and 19 atoms, respectively) are too large for determining accurate equilibrium structures, either by high-level ab initio methods or by experiments alone. We show in this work that the semiexperimental (SE) mixed estimation (ME) method offers a valuable alternative for equilibrium structure determinations in moderate-sized molecules such as these monosaccharides or other biochemical building blocks. The SE/ME method proceeds by fitting experimental rotational data for 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 later supplemented 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 to determine an equilibrium structure (rSE). We applied the ME method here to fructose and 2-deoxyribose e and checked the accuracy of the calculations for 2-deoxyribose against the high level ab initio rBO structure e fully 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.
Peer Review: SI
DOI: 10.1039/c6cp01842d
Sponsor: MINECO-FEDER CTQ2014-54464-R, CTQ2015-68148-C2
Publisher Version:
Language: eng
Rights: info:eu-repo/semantics/openAccess
An error occurred on the license name.
Appears in Collections:DEP63 - Artículos de revista

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