Conformations, vibrational frequencies and Raman intensities of short-chain fatty acid methyl esters using DFT with 6-31G(d) and Sadlej pVTZ basis sets

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of three short-chain fatty acid methyl esters (FAMEs) with the formula CnH2nO2 (n = 3-5). In all three FAMEs, the lowest energy conformer has a simple 'all-trans' structure but there are other conformers, with different torsions about the backbone, which lie reasonably close in energy to the global minimum. One result of this is that the solid samples we studied do not appear to consist entirely of the lowest energy conformer. Indeed, to account for the 'extra' bands that were observed in the Raman data but were not predicted for the all-trans conformer, it was necessary to add-in contributions from other conformers before a complete set of vibrational assignments could be made. Provided this was done, the agreement between experimental Raman frequencies and 6-31G(d) values (after scaling) was excellent, RSD = 12.6 cm(-1). However, the agreement between predicted and observed intensities was much less satisfactory. To confirm the validity of the approach followed by the 6-3 1 G(d) basis set, we used a larger basis set, Sadlej pVTZ, and found that these calculations gave accurate Raman intensities and simulated spectra (summed from two different conformers) that were in quantitative agreement with experiment. In addition, the unscaled Sadlej pVTZ, and the scaled 6-3 1 G(d) calculations gave the same vibrational mode assignments for all bands in the experimental data. This work provides the foundation for calculations on longer-chain FAMEs (which are closer to those found as triglycerides in edible fats and oils) because it shows that scaled 6-3 1 G(d) calculations give equally accurate frequency predictions, and the same vibrational mode assignments, as the much more CPU-expensive Sadlej pVTZ basis set calculations.

On linear extension operators

We construct a countable-dimensional Hausdorff locally convex topological vector space $E$ and a stratifiable closed linear subspace $F$ subset of $E$ such that any linear extension operator from $C_b(F)$ to $C_b(E)$ is unbounded (here $C_b(X)$ stands for the Banach space of continuous bounded real-valued functions on $X$).

Three constructive examples of separable pre-Hilbert spaces nonisomorphic to their closed hyperplanes

An example of a sigma -compact infinite-dimensional pre-Hilbert space H is constructed such that any continuous linear operator T: H --> H is of the form T = lambdaI + F for some lambda is an element of R and for a finite-dimensional continuous linear operator F. A class of simple examples of pre-Hilbert spaces nonisomorphic to their closed hyperplanes is given. A sigma -compact pre-Hilbert space H isomorphic to H x R x R and nonisomorphic to H x R is also constructed.

Integral completeness of locally convex spaces

A locally convex space X is said to be integrally complete if each continuous mapping f: [0, 1] --> X is Riemann integrable. A criterion for integral completeness is established. Readily verifiable sufficient conditions of integral completeness are proved.

On effective linearly ordered sets of comparison functions

Both the existence and the non-existence of a linearly ordered (by certain natural order relations) effective set of comparison functions (=dense comparison classes) are compatible with the ZFC axioms of set theory.

An infinite-dimensional separable pre-Hilbert space non-homeomorphic to any of its closed hyperplanes

An example is constructed of an infinite-dimensional separable pre-Hilbert space non-homeomorphic to any of its closed hyperplanes.

On stratifiable locally convex spaces

In the present paper we prove several results on the stratifiability of locally convex spaces. In particular, we show that a free locally convex sum of an arbitrary set of stratifiable LCS is a stratifiable LCS, and that all locally convex F'-spaces whose bounded subsets are metrizable are stratifiable. Moreover, we prove that a strict inductive limit of metrizable LCS is stratifiable and establish the stratifiability of many important general and specific spaces used in functional analysis. We also construct some examples that clarify the relationship between the stratifiability and other properties.

Some results on solvability of ordinary linear differential equations in locally convex spaces

Let $\Gamma$ be the class of sequentially complete locally convex spaces such that an existence theorem holds for the linear Cauchy problem $\dot x = Ax$, $x(0) = x_0$ with respect to functions $x: R\to E$. It is proved that if $E\in \Gamma$, then $E\times R^A$ is-an-element-of $\Gamma$ for an arbitrary set $A$. It is also proved that a topological product of infinitely many infinite-dimensional Frechet spaces, each not isomorphic to $\omega$, does not belong to $\Gamma$.