Force field and vibrational assignment for cyclobutane from a combination of ab initio calculations and experimental data

Bánhegyi, György; Fogarasi, Géza; Pulay, Péter

doi:10.1016/0166-1280(82)80146-2

Cited by 37 publications

(6 citation statements)

References 23 publications

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“…6 In short, it is clear that the C-H and C-D stretching modes of a pure hydrocarbon should provide a best possible case for both. The presence of two conformers 7 University of Illinois at Chicago. •University of Missouri-St. Louis.…”

Section: Discussionmentioning

confidence: 99%

Properties of ions and radicals derived from decacarbonyldimanganese, decacarbonylmanganeserhenium, and decacarbonyldirhenium by electron attachment and protonation in the gas phase

Meckstroth¹,

Ridge²

1985

J. Am. Chem. Soc.

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Mnz(CO)lo, ReMn(CO)lo, and Rez(CO)lo attach thermal electrons in the gas phase and lose either a CO or an M(C0)5 radical. The extent of M(C0)5 loss decreases in the order M I I~( C O )~~ > ReMn(CO)lo > Re2(CO)lo. No M(CO)5 loss is observed for Re2(CO)lo, and both Mn(CO), and Re(CO), are lost from ReMn(CO)lo. Assuming that there is no energy barrier for charge transfer between Re(CO), and Mn(CO)< leads to the conclusion that D(Re(CO),-Mn(CO),) < EA(MII(CO)~) N EA(Re(CO),. HCI and other acids fail to transfer a proton at an observable rate to Mn(CO),-, Re(CO),-, Mn2(C0)-, ReMn(CO)-, and Re2(C0)9-. Assuming this is because the proton transfers are endothermic leads to the conclusion that the proton affinities of the unreactive negative ions are less than that of C1-. Combining the conclusions about the radical electron affinities with proton affinity and bond strength data from the literature gives EA(Re(C0)J = EA(Mn(CO)5) 2.43 f 0.21 eV. The gas-phase electron-attachment processes are found to closely resemble the reactions of radiolytically produced solvated electrons. The proton affinities of Mn2(CO)lo, ReMn(CO)lo, and Re2(CO)lo are found to be 774 f 13, 794 f 6, and 805 f 5 kJ/mol, respectively. Comparison with proton affinities of M(CO)5CH3 species suggests that substituting a methyl group for M(CO), in the M2(CO)lo has very little effect on the proton affinity.(1) Elian, M.; Hoffmann, R. Inorg. Chem. 1975, 14, 1058-1076. Elian, M.; Chen, M. M. L.; Mingos, D. M. P.; Hoffmann, R. Ibid. 1976, 15, 1148-1 155. Schilling, B. E. R.; Hoffmann, R.; Lichtenberger, D. L.

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Section: Discussionmentioning

confidence: 99%

Properties of ions and radicals derived from decacarbonyldimanganese, decacarbonylmanganeserhenium, and decacarbonyldirhenium by electron attachment and protonation in the gas phase

Meckstroth¹,

Ridge²

1985

J. Am. Chem. Soc.

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“…The EELS spectrum of physisorbed molecules (Figure 6a) is in agreement with the FTIR and Raman spectra and the calculated assignments of the normal vibrational modes of chloroacetonitrile in the liquid phase. [21][22][23]41,42 The loss peaks at 348, 470, 750, 920, 1182, 1267, 1420, 1840, 2256, 2980, and 3070 cm -1 can be clearly resolved. Among them, the peaks at 3070 and 2980 cm -1 can be ascribed to the CH 2 asymmetric and symmetric stretching modes, respectively.…”

Section: Coexistence Of [2 + 2] Cycloaddition-like and Enelike Reacti...mentioning

confidence: 96%

“…Among them, the peaks at 3070 and 2980 cm -1 can be ascribed to the CH 2 asymmetric and symmetric stretching modes, respectively. 42 The CtN stretching mode appears at 2256 cm -1 . The peaks at 750 and 470 cm -1 can be assigned to the C-Cl stretching mode and the C-C-Cl skeletal bending mode, respectively.…”

Section: Coexistence Of [2 + 2] Cycloaddition-like and Enelike Reacti...mentioning

confidence: 99%

Switching from a [2 + 2] Cycloaddition-Like to an Ene-Like Reaction in Covalent Attachment of Halogenated Acetonitrile on Si(100)-2×1: Effect of Halogen Substituent

et al. 2010

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The adsorption of halogenated acetonitrile (X-CH 2 CtN, X ) F, Cl, Br) on Si(100)-2×1 has been studied using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculation. Fluoroacetonitrile chemisorbs on the Si(100)-2×1 surface via a CtN [2 + 2] cycloaddition-like reaction, while chloroacetonitrile is chemically bound to the Si surface through both CtN [2 + 2] cycloaddition-like and ene-like reactions. However, bromoacetonitrile was found to attach onto the surface exclusively through the ene-like reaction. The different reaction pathways of these halogenated compounds on the Si(100)-2×1 surface demonstrate that the halogen substitution groups play an important role in manipulating the reaction channels of bifunctional molecules, offering a great flexibility in surface reaction of silicon surfaces.

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“…However, bonds between different atoms define different, although parallel, straight lines. While the above relationships require zero intercepts, the data for actual molecules show that the D axis is crossed at values significantly different from zero, ranging between 24 and 52 kcal/mol.…”

mentioning

confidence: 97%

Quantitative relationship between bond dissociation energies, infrared stretching frequencies, and force constants in polyatomic molecules

Zavitsas¹

1987

J. Phys. Chem.

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at 2090 cm'1. Therefore, it is likely that the 2092-cm"1 band arises from decomposition of ferricyanide during oxidation of ferrocyanide. ConclusionWithin the limits of the model described above we conclude that adsorption of ferricyanide and ferrocyanide on metal electrodes is an important step in the heterogeneous electron-transfer reaction. It appears that ion pairing with alkali-metal cations may stabilize particular surface-adsorbate orientations. These orientations explain the nature of the spectra of the adsorbed species observed by Raman and infrared spectroscopies and the behavior of the spectra with changes in cation and electrode potential. The simplicity of the model should be noted. Actual surface-adsorbate interactions may be much more complex; thus, this model does not account for large changes in electronic structure which must occur upon adsorption and which must be important in determining the kinetics of the ferri/ferrocyanide redox reaction.However, the model can be used effectively to assess qualitatively the nature of the intramolecular interactions.

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Force field and vibrational assignment for cyclobutane from a combination of ab initio calculations and experimental data

Cited by 37 publications

References 23 publications

Properties of ions and radicals derived from decacarbonyldimanganese, decacarbonylmanganeserhenium, and decacarbonyldirhenium by electron attachment and protonation in the gas phase

Properties of ions and radicals derived from decacarbonyldimanganese, decacarbonylmanganeserhenium, and decacarbonyldirhenium by electron attachment and protonation in the gas phase

Switching from a [2 + 2] Cycloaddition-Like to an Ene-Like Reaction in Covalent Attachment of Halogenated Acetonitrile on Si(100)-2×1: Effect of Halogen Substituent

Quantitative relationship between bond dissociation energies, infrared stretching frequencies, and force constants in polyatomic molecules

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