Geometry of the optimized propanol and butanol monomers. Numbers index the various nearest-neighbor carbon-carbon lengths. Dark, grey, and white spheres denote oxygen, carbon, and hydrogen atoms, respectively.
CPs for the studied BuOH isomers (calculated data for trimers are shown). In the scale of the main figure the differences in the profiles are too small to be seen. The inset shows the region around the peak of the profile. Solid line: ; dashed line: sec-BuOH; dashed-dotted line: iso-BuOH.
Influence of the basis set and XC scheme on the difference CP between and iso-PrOH dimers. The experimental data are given by the black open circles with the error bars. The upper curves are offset vertically for clarity. In the basis set comparisons the XC scheme was RPBE. In the comparisons of XC schemes the basis set was TZVP-A.
Experimental CP differences : (circles), (squares), and (triangles). The solid vertical lines indicate the positions of the maxima and minima in the curves. The dashed vertical lines indicate the positions of the zero crossings.
CP differences using optimized monomers (dot-dashed lines), dimers (dashed lines), and trimers (solid lines) compared to the experimental data (markers). The method for the computed CPs is RPBE/cc-pV6Z. The curves have been shifted vertically for clarity.
C–C, C–O, and O–H covalent bond lengths (Å) for the computed propanol and butanol oligomers. The C–C bond lengths are indexed as indicated in Fig. 1 and the monomer values are given. Each entry of the C–O and C–H distances comprises six values: . The first value is the bond length for the monomer . The rest of the values are the bond lengths for the dimer and trimer given as the difference to the corresponding bond length of the monomer (in units of ). , , and denote the acceptor, donor-acceptor, and donor molecules, respectively. constr. denotes a calculation in which the distance is fixed to to represent a liquidlike geometry. The TraPPE-UA force field parameters are given for comparison.
Intermolecular O–O distances (Å) for the computed propanol and butanol dimers and trimers.
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