ABSTRACT
A novel Raman jet-spectrometer is used to study the Fermi resonance between the OH bending overtone and OH stretching fundamental in small cyclic water clusters (H2O)n with n = 3, 4, 5. The new setup features a recirculating vacuum system which reduces the gas consumption by 2 to 3 orders of magnitude and enables long-term measurements of very weak Raman signals. Raman spectra measured from highly diluted expansions with unprecedented signal-to-noise ratio are presented and cluster-specific intensity ratios and effective coupling constants are derived using Markov-Chain Monte-Carlo methods, yielding a high probability for an almost "perfect" resonance for the tetramer and pentamer, i.e. a close frequency match of bend overtone and stretch fundamental with intensity ratios close to 1, but a larger coupling constant for the trimer, with best estimates close to W5 â² 50 cm-1 < W4 â² 60 cm-1 < W3 ≈ 65 cm-1.
ABSTRACT
Phenylacetylene offers two similarly attractive π binding sites to OH containing solvent molecules, the phenyl ring and the acetylenic triple bond. By systematically varying the solvent molecule and by methylating aromatic or acetylenic CH groups, the docking preference can be controlled. It ranges from almost exclusive acetylene docking to predominant phenyl docking, depending on how electron density is deposited into the conjugated system and how large the London dispersion interaction is. FTIR spectroscopy of supersonic jet expansions is used to observe the competitive docking preferences in phenylacetylene and some of its methylated derivatives. A new data evaluation procedure that estimates band strength uncertainties based on a Monte Carlo approach is introduced. We test how well two density functionals (B3LYP-D3 and M06-2X) in combination with a def2-TZVP basis set are able to describe the docking switch. B3LYP-D3 is slightly biased towards acetylenic hydrogen bond docking and M06-2X is strongly biased towards phenyl hydrogen bond docking. More accurate theoretical predictions are invited and some previous experimental assignments are questioned.
ABSTRACT
Linear alkanes CnH2n+2 in vacuum isolation are finite models for an infinite polyethylene chain. Using spontaneous Raman scattering in supersonic jet expansions for n = 13-21 in different spectral ranges, we determine the minimal chain length nh for the cohesion-driven folding of the preferred extended all-trans conformation into a hairpin structure. We treat fully stretched all-trans alkanes as molecular "nanorods" and derive Young's modulus E for the stretching of an isolated single-strand polyethylene fibre by extrapolating the longitudinal acoustic mode to infinite chain length. Two key quality parameters for accurate intra- and intermolecular force fields of hydrocarbons (nh = 18 ± 1, E = 305 ± 5 GPa) are thus derived with high accuracy from experimental spectroscopy.
ABSTRACT
Mother of all folding: cold isolated linear alkanes C(n)H(2n+2) prefer an extended all-trans conformation before cohesive forces between the chain ends induce a folded hairpin structure for longer chains. It is shown by Raman spectroscopy at 100-150 K that the folded structure becomes more stable beyond n(C) = 17 or 18 carbon atoms. High-level quantum-chemical calculations yield n(C) = 17 ± 1 as the critical chain length.
ABSTRACT
Proton tunneling between the two equivalent structures of malonaldehyde through a substantial barrier is accelerated by more than a factor of 3 to approximately 0.24 ps by OH-bend excitation in phase with suitable motions of the molecular backbone. This is derived from a combined FTIR and Raman spectroscopy study in supersonic jets and rare gas matrices and compared to previous theoretical predictions.
