Theory of new states, FEXs, Fast-formed EXcited states by the combination of an IR photon and water.

In the IR spectra of water on polyethylene, polypropylene and polytetrafluoroethylene frequent and substantial negative peaks occurred and are explained by a theoretical analysis. New states, FEXs, Fast-formed EXcited states are formed by the combination of an IR photon and water and are now made manifest by inefficient energy transfer to the polymer combined with limited energy transfer to the small (0.5-1.

Negative infrared bands-A new phenomenon in the vibrational spectroscopy of water oligomers.

Infrared spectra of small amounts of water on the "hydrophobic" polymers, polyethylene (PE), polypropylene (PP) and polytetrafluoroethylene (PTFE), include many negative infrared bands that become positive with increasing temperature. The new species that the bands represent must arise through absorption of the incident radiation to form short-lived femtosecond states that disappear by (a) induced (Einstein) emission, thus leading to negative IR bands, or (b) fragmentation with loss of vibrational energy or (c) are replaced by an infrared excited state. In addition, we must note that polyethylene, polypropylene and polytetrafluoroethylene carry water! and many water oligomers (chair, boat, and prism hexamer) are easily observed.

Neutral dipole-dipole dimers: A new field in science.

Dimer formation with dipole neutralization produces species such as low polarity water (LPW) compatible with hydrophobic surfaces (Phys. Chem. Chem.

Low polarity water, a novel transition species at the polyethylene-water interface.

The bridge between water repelling and water-attracting regions is recognized here as low polarity water, a novel "neutral" form of water; its identity as a dipole-dipole water dimer is supported by spectroscopic evidence of its presence in thin films of water on a polyethylene surface. High resolution (0.5 cm(-1)), low signal energies (Sg 100) and short scans (0.

N-methyl-trimethylacetamide in thin films displays infrared spectra of π-helices, with visible static and dynamic growth phases, and then a β-sheet.

The simplest (minimal) peptide model is HCONHCH3. An increase in the π-helix content with increased substitution in the acyl portion suggested the examination of N-methyl-trimethylacetamide) (NMT). NMT displays spectra, in which there is evolution of a set of helices defined by their amide I maxima near 1686 (3(10)), 1655 (first π), and, most importantly, at 1637 cm(-1) (π).

N-alkylacylamides in thin films display infrared spectra of 3₁₀-, α-, and π-helices with visible static and dynamic growth phases.

A peptide model is a physical system containing a CONH group, the simplest being HCONHCH3 , N-methylformamide (NMF). We have discovered that NMF and N-methylacetamide (NMA), which form hydrogen-bonded oligomers in thin films on a planar AgX fiber, display infrared (IR) spectra with peaks like those of polypeptide helices. Structures can be assigned by their amide I maxima near 1672 (3(10)), 1655 (3(10)), 1653 (α), 1655 (π), and 1635 cm(-1) (π), which are the first IR data for the π-helix.

Surface electrostatic immobilization of thin layers of water on silver halide. Experimental and calculated infrared spectrum of cyclic trimer of water and a ponderal isotope effect.

Evaporation of water on a planar AgX surface leads to a strongly bound monolayer for which IR spectra display the marker peaks for modest numbers of oligomers. From 700-1800 spectra for each isotopomer, H(2)O(16) and H(2)O(18), a pair was selected with moderate intensity at 1616 cm(-1) (a peak reported for the cyclic trimer of water) from the monolayer portion of the experiment. Every selected spectrum had lesser peaks for other oligomers.

N-methylformamide, a hyperplectic model for peptides in thin film infrared spectroscopy on planar AgX.

N-methylformamide (NMF), the simplest model for peptides, exhibits hyperplectic (both simple and complex) behavior as revealed by thin film infrared spectroscopy on planar AgX [AgCl:AgBr] fiber. IR spectra (0.1 s scans) of 10 microg NMF/dichloromethane(DCM) under N(2) flow first show NMF monomer, dimers, and trimers, which then form surface-organized NMF oligomers as pseudocrystals (P(n)) of increasing length and intensity to P(12).

Thin-film infrared spectroscopy of acetonitrile.

Acetonitrile and [D3]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole-dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C--N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH3CN 2252 cm(-1), CD3CN 2262 cm(-1)) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD3CN resulting in an increase in the CN band intensity.

Molecule-enhanced surface-enhanced infrared absorption spectroscopy (MOSEIRA).

Surface-enhanced infrared absorption spectroscopy (SEIRA) of methanol, ethanol, 1-propanol, and 2-propanol in thin films on planar silver halide (AgX) fibers under slow N(2) flow using 1 sec scans reveals structure in absorbance-time plots. The absorption intensities show extra enhancements (3x) in the absorbance (O--H stretch) ascribed to oligomers present at the AgX surface (molecule enhanced, thus MOSEIRA). This is above those due to amplification (40x, 20 reflections) and enhancement (30x, image dipoles or surface phonon polaritons).

Sequence of Reactant Combination Alters the Course of the Staudinger Reaction of Azides with Acyl Derivatives. Bimanes. 30.

The Staudinger reaction of azides has now been followed by NMR and other spectroscopic techniques. syn-(Azidomethyl,methyl)(methyl,methyl)bimane (1) and Ph(3)P form a triazaphosphadiene intermediate 2 and then the bimane P-triphenyliminophosphorane 3. The iminophosphorane reacts with an acyl chloride to yield an iminophosphonium salt 4 which then forms the oxazaphosphetane 13.