A Spectroscopic and Computational Investigation of the Conformational Structural Changes Induced by Hydrogen Bonding Networks in the Glycidol-Water Complex

作者：Conrad A R; Teumelsan N H; Wang P E; Tubergen M J^*

来源：Journal of Physical Chemistry A, 2010, 114(1): 336-342.

DOI：10.1021/jp908351u

Rotational spectra were recorded in natural abundance for the (13)C isotoporners of two conformers of glycidol. Moments of inertia from the (13)C isotoporners were used to calculate the substitution coordinates and C-C bond lengths of two glycidol monomer conformations. The structures of seven different conformational minima were found from A initio (MP2/6-311++G(d,p)) optimizations of glycidol-water. The rotational spectrum of glycidol-water wits recorded using microwave spectroscopy, and the rotational constants were determined to be A = 3902.331 (11) MHz, B = 2763.176 (3) MHz, and C = 1966.863 (3) MHz. Rotational spectra were also recorded for glycidol-H(2)(18)O, glycidol-D(b)OH, and glycidol-d(O)-D(2)O. The rotational spectra were assigned to the lowest-energy A initio structure, and the structure was improved by fitting to the experimental moments of inertia. The best-fit structure shows evidence for structural changes in glycidol to accommodate formation of the intermolecular hydrogen bonding network: the O-C-C-O torsional angle in glycidol was found to increase from 40.8 degrees for the monomer to 49.9 degrees in the water complex.

• 出版日期2010-1-14