Extension of panoramic cluster jet spectroscopy into the far infrared: Low frequency modes of methanol and water clusters

Liu, Yaqian; Weimann, Marcus; Suhm, Martin A.

doi:10.1039/b402379j

Cited by 33 publications

(35 citation statements)

References 34 publications

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“…Regarding the origin of the low-frequency bands near 200 cm −1 , there have been several simulation and experimental reports on the existence of translational bands even in the small water clusters 28–30 , which have a very similar size compared to our nanomeniscus system. Moreover, the heating-induced correlated decrease between the low (lattice vibration) and high (OH stretching) frequency bands (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 87%

Ice-VII-like molecular structure of ambient water nanomeniscus

2019

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Structural transformations originating from diverse rearrangements of the hydrogen bonding in water create various phases. Although most phases have been well investigated down to the molecular level, the molecular structure of the nanomeniscus, a ubiquitous form of nanoscale water in nature, still remains unexplored. Here, we demonstrate that the water nanomeniscus exhibits the stable, ice-VII-like molecular structure in ambient condition. Surface-enhanced Raman spectroscopy on trace amounts of water, confined in inter-nanoparticle gaps, shows a narrowed tetrahedral peak at 3340 cm-1 in the OH-stretching band as well as a lattice-vibrational mode at 230 cm-1. In particular, the ice-VII-like characteristics are evidenced by the spectral independence with respect to temperature variations and differing surface types including the material, size and shape of nanoparticles. Our results provide un unambiguous identification of the molecular structure of nanoconfined water, which is useful for understanding the molecular aspects of water in various nanoscale, including biological, environments.

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Section: Resultsmentioning

confidence: 87%

Ice-VII-like molecular structure of ambient water nanomeniscus

2019

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“…A reported band origin of 3681.5 cm −1 for the monomer OH stretching band based on the center of gas-phase Q-branches 34,35 has been employed in a range of cluster studies. 19,21,[35][36][37][38] A band origin at 3686 cm −1 has subsequently been established by complementary Raman and infrared studies of jet-cooled methanol. 22,39 This value corresponds to the high-frequency component of the jet-Raman spectrum 39 and the absorption maximum in the jet-FTIR spectrum 22 and agrees well with the band origin of 3685 cm −1 obtained from a high-resolution rovibrational analysis of this strongly coupled torsion-vibration system.…”

Section: Methanol Isolated In Supersonic Jet Expansionsmentioning

confidence: 97%

The effect of hydrogen bonding on torsional dynamics: A combined far-infrared jet and matrix isolation study of methanol dimer

Kollipost

Andersen

Heimdal

et al. 2014

The Journal of Chemical Physics

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The effect of strong intermolecular hydrogen bonding on torsional degrees of freedom is investigated by far-infrared absorption spectroscopy for different methanol dimer isotopologues isolated in supersonic jet expansions or embedded in inert neon matrices at low temperatures. For the vacuum-isolated and Ne-embedded methanol dimer, the hydrogen bond OH librational mode of the donor subunit is finally observed at ~560 cm(-1), blue-shifted by more than 300 cm(-1) relative to the OH torsional fundamental of the free methanol monomer. The OH torsional mode of the acceptor embedded in neon is observed at ~286 cm(-1). The experimental findings are held against harmonic predictions from local coupled-cluster methods with single and double excitations and a perturbative treatment of triple excitations [LCCSD(T)] and anharmonic. VPT2 corrections at canonical MP2 and density functional theory (DFT) levels in order to quantify the contribution of vibrational anharmonicity for this important class of intermolecular hydrogen bond vibrational motion.

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“…140 Librational motions of the central hydrogen away from the hydrogen bond are very sensitive to cluster size, symmetry, bulkiness, 141 bond strength and deuteration. 139 Starting as hindered rotations well below 100 cm À1 , they can be shifted up to 1000 cm À1 due to the hydrogen bond constraint. 14,139,[142][143][144] Thus, they have a major influence on the zero-point energy and spectral properties of a complex.…”

Section: Double and Triple Bondsmentioning

confidence: 99%

Femtisecond single-mole infrared spectroscopy of molecular clusters

Suhm

Kollipost

2013

Phys. Chem. Chem. Phys.

136

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The sensitivity limitations of Fourier transform infrared (FTIR) spectroscopy for the detection of molecular clusters formed in rarefied gas expansions can be overcome by synchronizing intense gas pulses at a low duty cycle with rapid interferometer scans. This turns the broadband FTIR approach into a universal cluster spectroscopy tool applicable from the far (200 cm(-1)) to the near (8000 cm(-1)) IR. It nicely complements more selective and more restricted laser-based techniques and it provides a gas-phase variant of the matrix-isolation method, the main drawback being substance consumption. A survey over the capabilities, limitations and perspectives of this high-throughput nozzle approach to cluster FTIR spectroscopy is given.

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Extension of panoramic cluster jet spectroscopy into the far infrared: Low frequency modes of methanol and water clusters

Cited by 33 publications

References 34 publications

Ice-VII-like molecular structure of ambient water nanomeniscus

Ice-VII-like molecular structure of ambient water nanomeniscus

The effect of hydrogen bonding on torsional dynamics: A combined far-infrared jet and matrix isolation study of methanol dimer

Femtisecond single-mole infrared spectroscopy of molecular clusters

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