Vibrational predissociation spectra of size selected methanol clusters: New experimental results

Buck, U.; Ettischer, Ingo

doi:10.1063/1.475391

Cited by 60 publications

(62 citation statements)

References 22 publications

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“…19 Note, however, that the results for the relative intensities of the OH stretch modes of the heptamer again indicate an approximate C 7h symmetry like behavior. Because of the S 8 symmetry of the octamer only two infrared active modes are calculated for CO and OH stretch modes.…”

Section: Frequency Shiftsmentioning

confidence: 89%

“…19 The cluster approach is a simple tool for calculating frequency shifts in quite complicated systems and yields reliable results providing that accurate intra-and intermolecular interaction potentials are used.…”

Section: Discussionmentioning

confidence: 99%

“…18 It is noted that the new experimental results up to the nonamer will be presented in a forthcoming paper. 19 All calculations for methanol clusters based on separated intra-and intermolecular potentials [7][8][9] were carried out using the Optimized Potential for Liquid Simulation ͑OPLS͒ by Jorgensen 20 for the intermolecular part. While a qualitative agreement between measured and calculated data was found a͒ Present address: Department of Chemistry, University of Nottingham, Notthingham NG7 2RD, England.…”

Section: Introductionmentioning

confidence: 99%

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Structure and vibrational spectra of methanol clusters from a new potential model

Buck

Siebers

Wheatley

1998

The Journal of Chemical Physics

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105

104

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The structures and vibrational spectra of small methanol clusters from dimer to decamer have been calculated using a newly developed intermolecular potential which is essentially based on monomer wave functions. Special care has been taken for the description of the electrostatic interaction using a distributed multipole representation and including a penetration term. In addition, the potential model consists of repulsion, dispersion, and induction terms. Based on this potential model cluster structures have been calculated. The lowest energy dimer configuration is linear, while from trimer to decamer for the most stable structures ring configurations were found. Tetramer, hexamer, and octamer have S4-, S6-, and S8-symmetry, respectively. Vibrational spectra of the CO stretch and the OH stretch mode have been determined in the harmonic and in the anharmonic approximation using perturbation theory and variational calculations. Up to the tetramer the experimental spectra of the CO stretch mode are well reproduced, for larger clusters an increasing blueshift with respect to the experimental evidence is found. The experimental data for the OH stretch mode of the dimer are fairly well reproduced in all approximations, however, the spectrum of the trimer can only be reproduced using the variational calculation which includes Darling–Dennison resonance terms.

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Section: Frequency Shiftsmentioning

confidence: 89%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure and vibrational spectra of methanol clusters from a new potential model

Buck

Siebers

Wheatley

1998

The Journal of Chemical Physics

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105

104

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“…The BM m clusters include methanols that are involved as π H-bond donor (BM 1 ), OH ... O donor (BM 2,3 ), OH acceptor/π donor (BM 2,3 ), and OH ... O acceptor/donor methanols (BM [3][4][5]. The calculations on M m and BM m clusters (Figure 5a) faithfully reproduce the experimental shifts for these H-bonding site types and extend the range of H-bonding site occupation to include A, AA, and AAD methanols.…”

Section: Discussionmentioning

confidence: 99%

C−H Stretch Modes as a Probe of H-Bonding in Methanol-Containing Clusters

et al. 1999

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Resonant ion-dip infrared spectroscopy has been used to record infrared spectra of a series of benzene-(methanol) m clusters with m ) 1-5 in the O-H and C-H stretch regions. Previous work has used the O-H stretch region as a probe of the H-bonding topologies of these clusters, from which it was deduced that benzene-(methanol) 1-3 contain H-bonded methanol chains and benzene-(methanol) 4-6 H-bonded methanol cycles. In the present work, the C-H stretch fundamentals of the methyl group of methanol and the aryl C-H groups of benzene are studied. While benzene's C-H stretch Fermi triad is virtually unchanged in frequency from one cluster to the next, the methyl C-H stretch vibrations undergo systematic wavenumber shifts characteristic of the H-bonding arrangement for each methanol in the cluster. Density functional theory calculations on the pure methanol and benzene-(methanol) m clusters faithfully reproduce the directions and approximate magnitudes of the observed shifts and provide a basis for assignment of the observed transitions to acceptor, donor, and acceptor-donor methanol subunits. The experimental results on the ν 2 fundamental of methanol in benzene-(methanol) 1-5 show characteristic frequency shifts due to (i) donor (D, -20 to -15 cm -1 ), (ii) acceptor-donor (AD) and π donor (π) (-6 to -9 cm -1 ), and (iii) OH ... O acceptor/π donor (Aπ, -4 to +2 cm -1 ). Calculations on (methanol) m and benzene-(methanol) m clusters extend the predictions to include characteristic shifts for (iv) double-acceptor/single-donor (AAD, +5 to +15 cm -1 ), (v) single-acceptor (A, +15 to +30 cm -1 ), and (vi) double-acceptor (AA) (+20 to +30 cm -1 ). FTIR spectra of liquid methanol and of binary solutions of methanol with acetone-d 6 , CDCl 3 , and D 2 O indicate that methanol's CH stretch frequency shifts reflect methanol's H-bonding environment in solution as well.

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“…The experiments have been carried out in a molecular beam machine which has been described in detail previously [195,196]. The large water clusters are produced in a supersonic expansion of mixed and pure water vapour at 2-22 bar through nozzles of conical shape with diameters between 50 and 90 mm, opening angles between 20 and 41 , and 2-6 mm length.…”

Section: Overviewmentioning

confidence: 99%

Solid water clusters in the size range of tens–thousands of H₂O: a combined computational/spectroscopic outlook

Buch

Bauerecker²,

Devlin³

et al. 2004

International Reviews in Physical Chemistry

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224

294

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2004) Solid water clusters in the size range of tens-thousands of H 2 O: a combined computational/spectroscopic outlook, A joint computational and experimental effort was directed towards the understanding of large solid water clusters. The computations included structure optimizations and calculations of OH stretch spectra for select sizes in the range n ¼ 20-931. The measurements focused predominantly on OH stretch spectroscopy as a function of mean cluster size. FTIR spectra are discussed for the size range of tens to hundreds-of-thousands of molecules. Photofragment spectroscopy in molecular beams is shown to be a sensitive probe of the outer cluster surfaces. The crucial element of the different experimental approaches is the control and the estimation of the mean cluster sizes. The combined experimental and computational results are consistent with the physical picture of quasispherical nanocrystals with disordered reconstructed surface layers. The surface reconstruction can be viewed as the outcome of recombination of surface dangling atoms, to increase the number of hydrogen bonds. The hydrogen bonds within the mostly crystalline subsurface layer are stretched by the interaction with the disordered component. The emergence of the (strained) crystal core occurs at a size of a few hundred H 2 O. Smaller clusters are described as compactamorphous.

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Vibrational predissociation spectra of size selected methanol clusters: New experimental results

Cited by 60 publications

References 22 publications

Structure and vibrational spectra of methanol clusters from a new potential model

Structure and vibrational spectra of methanol clusters from a new potential model

C−H Stretch Modes as a Probe of H-Bonding in Methanol-Containing Clusters

Solid water clusters in the size range of tens–thousands of H₂O: a combined computational/spectroscopic outlook

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Vibrational predissociation spectra of size selected methanol clusters: New experimental results

Cited by 60 publications

References 22 publications

Structure and vibrational spectra of methanol clusters from a new potential model

Structure and vibrational spectra of methanol clusters from a new potential model

C−H Stretch Modes as a Probe of H-Bonding in Methanol-Containing Clusters

Solid water clusters in the size range of tens–thousands of H2O: a combined computational/spectroscopic outlook

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Solid water clusters in the size range of tens–thousands of H₂O: a combined computational/spectroscopic outlook