Vibrational spectra of crystalline HCCN, DCCCN, ClCCCN, BrCCCN, and ICCCN

Nolin, C.; Weber, J.V.; Savoie, Rodrigue

doi:10.1002/jrs.1250050104

Cited by 8 publications

(5 citation statements)

References 20 publications

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“…The structure , and the vibrational spectra − of the cyanoacetylene monomer are well-known. Similarly, the vibrational spectra of cyanoacetylene in the solid were quite thoroughly investigated. ,, However, apart from several more accurate investigations of the cyanoacetylene monomer, ,− only a few ab initio geometry optimizations of the linear cyanoacetylene dimer performed at the self-consistent field (SCF) level are available from the theoretical side. , To the best knowledge of the author, ab initio calculations on the vibrational spectrum of the cyanoacetylene dimer have not yet been reported, nor are there any theoretical studies available in the literature that deal with the structure and the vibrational spectra of larger cyanoacetylene clusters.…”

Section: Introductionmentioning

confidence: 99%

Linear and Cyclic Clusters of Hydrogen Cyanide and Cyanoacetylene: A Comparative ab Initio and Density Functional Study on Cooperative Hydrogen Bonding

Karpfen

1996

J. Phys. Chem.

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The equilibrium structures, the stabilization energies, the harmonic vibrational spectra, and the infrared intensities of linear and cyclic hydrogen cyanide, (HCN) n , and cyanoacetylene oligomers, (HC3N) n , were calculated at the ab initio self-consistent field and at the Møller−Plesset second-order level, as well as with the aid of a density functional method. Several extended basis sets were applied. The systematic modifications of the most important properties characteristic for the C−H- - -N hydrogen bond in these two series of intermolecular clusters, in particular, the intermolecular distances, R(H- -N), the intramolecular distances, R(C−H), the interaction energies per hydrogen bond, with and without zero-point energy corrections, the C−H stretching frequencies, ν(C−H), and their corresponding infrared intensities were monitored as a function of the oligomer size and are discussed in detail. The mode of convergence to the infinite chain limit is described and found to be qualitatively quite similar in both systems. From a quantitative point of view, all features usually attributed to hydrogen-bond nonadditivity are somewhat weaker for the cyanoacetylene clusters, mainly a consequence of the molecular size. Tentative assignments are suggested for the infrared active vibrations of larger cyclic cyanoacetylene clusters.

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Section: Introductionmentioning

confidence: 99%

Linear and Cyclic Clusters of Hydrogen Cyanide and Cyanoacetylene: A Comparative ab Initio and Density Functional Study on Cooperative Hydrogen Bonding

Karpfen

1996

J. Phys. Chem.

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“…Its Raman spectroscopy has also been studied. 5,6 Linearity of the molecule was confirmed with Xray diffraction measurements. 7 Bieri et al and Kuhn et al measured the photoelectron spectra.…”

Section: Introductionmentioning

confidence: 74%

Photoisomerization of IC3N — An experimental and theoretical study

Guzik

Gronowski

Turowski

et al. 2020

Journal of Photochemistry and Photobiology A: Chemistry

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J o u r n a l P r e-p r o o f Highlights  VUV photolysis of IC3N in argon matrix leads to IC2NC and ICNC2 isomers  IRC calculations show reaction paths leading to discovered isomers  IC3N ions and radical are not formed in detectable amounts for the IR absorption ABSTRACT: Here we present the results of a joint spectroscopic and quantum chemical study on the photochemistry of 3-iodo-2-propynenitrile (iodocyanoacetylene, IC3N). Vacuum-UV photolysis of the compound isolated in solid argon was explored. Calculations, carried out at the DFT and/or coupled-cluster level of theory, provided essential data concerning the thermodynamic stabilities, vibrational and electronic energy levels, ionization potentials, and electron affinities of IC3N-stoichiometry isomers and ions. The photochemical formation of thus far unknown species IC2NC and ICNC2 has been evidenced by the experiment and rationalized based on a detailed theoretical approach, involving the excited-state potential energy surfaces.

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“…From infrared − and Raman , experiments on solid cyanoacetylene, it is known that the C−H stretching modes in the extended linear hydrogen-bonded chains are found to be shifted by −123 and −118 cm -1 , respectively, relative to the monomer. It is to be expected that none of the smaller clusters treated in this work and measured in the gas phase should display larger red shifts in the C−H stretching region.…”

Section: Resultsmentioning

confidence: 99%

“…The complete vibrational analysis also showed that apart from the C-H-stretching region, the region of the CCH-bending modes (660-750 cm -1 ) appears most promising for gaining additional information to help in the assignment problem and in the identification of the clusters present in the vapor phase. It is well-known 47,48 that from the monomer (663 cm -1 ) to the crystal (749 cm -1 ), a blue shift of 86 cm -1 takes place for the CCH-bending mode. The calculations demonstrated that sufficiently different blue shifts can be expected for the various cluster types.…”

Section: Discussionmentioning

confidence: 97%

Ab Initio Studies on Cyanoacetylene Oligomers: Rings and Chains versus Stacked Clusters

Karpfen

1998

J. Phys. Chem. A

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The structures and the vibrational spectra of cyanoacetylene clusters were investigated with the aid of ab initio Møller−Plesset second-order calculations using large polarized basis sets. In addition to ring- and chainlike structures, stacked non-hydrogen-bonded configurations, in which chainlike oligomers are oriented in an antiparallel fashion, were investigated. Particular emphasis has been given to a more thorough investigation of selected sections of the energy surface of the cyanoacetylene dimer, including the search for parallel and antiparallel stacked structures and for π-type hydrogen-bonded configurations. This search revealed that apart from the linear dimer which corresponds to the energetically most stable dimer, a second minimum corresponding to a C 2 h stacked antiparallel dimer is quite close in energy, whereas π-type hydrogen-bonded configurations and parallel but slipped stacked arrangements are barely bound. The relatively high stability of the antiparallel stacked dimer has the consequence that larger stacked clusters, e.g., tetramers and hexamers, are likely to be of similar stability as the corresponding cyclic oligomers or are even the dominant species and that both, stacked and cyclic configurations, are significantly more stable than linear clusters from the tetramers on. Most of the experimentally observed infrared-active C−H stretching frequencies could be successfully assigned to particular oligomers.

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Vibrational spectra of crystalline HCCN, DCCCN, ClCCCN, BrCCCN, and ICCCN

Cited by 8 publications

References 20 publications

Linear and Cyclic Clusters of Hydrogen Cyanide and Cyanoacetylene: A Comparative ab Initio and Density Functional Study on Cooperative Hydrogen Bonding

Linear and Cyclic Clusters of Hydrogen Cyanide and Cyanoacetylene: A Comparative ab Initio and Density Functional Study on Cooperative Hydrogen Bonding

Photoisomerization of IC3N — An experimental and theoretical study

Ab Initio Studies on Cyanoacetylene Oligomers: Rings and Chains versus Stacked Clusters

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