Vibrational predissociation spectra of size selected hydrazine clusters: Experiment and calculations

Beu, Titus A.; Buck, U.; Ettischer, Ingo; Hobein, M.; Siebers, J. G.; Wheatley, Richard J.

doi:10.1063/1.473707

Cited by 18 publications

(32 citation statements)

References 25 publications

(35 reference statements)

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“…We call this procedure the cluster approach in contrast to other methods where the intermolecular interaction and the intramolecular anharmonicity are treated as a quantum mechanical perturbation and which thus start from the harmonic frequencies of the bare molecule. 8,9 Measurements and calculations have been conducted for various molecular clusters including SF 6 , 10-12 hydrazine, 13,14 and last but not least methanol clusters. For the latter one experimental data are available for the CO stretch mode 15 from dimer to hexamer and for the OH stretch mode for the dimer 16,17 and the trimer.…”

Section: Introductionmentioning

confidence: 99%

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

Buck

Siebers

Wheatley

1998

The Journal of Chemical Physics

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: Introductionmentioning

confidence: 99%

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

Buck

Siebers

Wheatley

1998

The Journal of Chemical Physics

104

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“…This approach has been applied to obtain the repulsion component in a systematic model potential for hydrazine clusters [6,7], with a proportionality constant being derived from matching the estimated binding energy of the complex. The correlation we obtain between the overlap and exchange repulsion in our system adds to the evidence from (F&.…”

Section: Resultsmentioning

confidence: 99%

“…Examples of the applications of this method are the model potential for the Li+-H20 complex [37], where the charge density overlap integral was calculated at a number of geometries and subsequently fitted to various functional forms (both isotropic and anisotropic), as well as model potentials for Na+-H20 and H20-H20 [38], where a similar fit of the charge density overlap integral to an anisotropic atom-atom function as part of a systematic potential correctly reproduced thermodynamic properties of the solvation of sodium ions in water clusters. The overlap method was applied recently with success also to produce the repulsive component of a potential which accounted for the spectroscopy of the hydrazine dimer [6,7]. This advantage of the overlap assumption is particularly marked for correlated wavefunctions, the use of which adds very little extra cost for the overlap calculations in contrast with the huge increase in computational requirements of both supermolecule and symmetry-adapted perturbation calculations.…”

Section: Introductionmentioning

confidence: 98%

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Use of molecular overlap to predict intermolecular repulsion in N ··· H—O hydrogen bonds

1998

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The overlap of the monomer charge distributions is used to derive atom-atom intermolecular repulsion models for N . . H and N . . ' 0 to model the hydrogen bonds formed between methylcyanide/methanol and pyridine/methanol. The use of the overlap approximation allows the repulsion contribution to be assigned to specific atomic pairs, and the anisotropic form to be derived analytically. The resulting models are tested against intermolecular perturbation theory calculations of the exchange-repulsion surface, in the regions sampled by these N . . H-0 hydrogen bonds in molecular crystal structures. Such models readily reproduce the repulsion surface within a 5% rms error, with the main error being attributable to the overlap approximation. The anisotropy of the atom-atom repulsion in these hydrogen bonds is small and the expansion converges slowly. However, the methodology shows that considering the overlap is a useful method of assigning the repulsion between organic molecules into atomic contributions and estimating the isotropic and anisotropic parameters, which can be applied to larger systems where accurate ab initio calculation of the potential energy surface is not feasible.

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“…1). Beu et al [9,10]. determined the binding energies and the antisymmetric NH 2 wagging modes for three dimer structures of hydrazine, making use of their intermolecular potential model.…”

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confidence: 99%

Theoretical study of chiral discrimination in the hydrogen bonding complexes of the hydrazine dimer

Zhou

2004

Int J of Quantum Chemistry

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ABSTRACT:In this work, the discrimination of different chiral forms of the hydrazine dimer were investigated using Density Functional Theory (DFT) and secondorder Moller-Plesset Perturbation (MP2) theory at basis set levels from 6-31g to 6-31ϩϩg(d,p). Four chiral structures were studied. The optimized geometric parameters, interaction energies, and chirodiastatic energy for various isomers at different levels were estimated. Finally, the solvent effects on the geometries of the hydrazine dimers were also investigated using self-consistent reaction-field (SCRF) calculations at the B3LYP/6-31ϩϩg(d,p) level. The results indicate that the polarity of the solvent has played an important role in the structures and relative stabilities of different isomers.

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Vibrational predissociation spectra of size selected hydrazine clusters: Experiment and calculations

Cited by 18 publications

References 25 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

Use of molecular overlap to predict intermolecular repulsion in N ··· H—O hydrogen bonds

Theoretical study of chiral discrimination in the hydrogen bonding complexes of the hydrazine dimer

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