Vibrational spectra and normal coordinate calculations for cis- and trans-1,2-dideuteriocyclobutanes

Annamalai, A.; Keiderling, T. A.

doi:10.1016/0022-2852(85)90050-5

Cited by 20 publications

(15 citation statements)

References 19 publications

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“…Our fitting suggest that A and C, and quantum of CH 2 wag+twist+ring stretch, and 1 quantum of CH 2 rock+twist, using the r-'tation of Annamalai and Keiderling. 42 The dark state identified is consistent with previous studies that the CH 2 rock couples well to the puckering motion.…”

Section: Discussionsupporting

confidence: 90%

“…The coupled dark state is identified to be the state with 1 quantum of ring stretch (ring breathing), 1 quantum of CH 2 wag+twist+ring stretch, and 1 quantum of CH 2 rock+twist, using the notation of Annamalai and Keiderling. 42 Each of the four perturbed states are then further coupled to a bath of dark states with small coupling matrix elements, which lead to four overlapping, peak-fractionated bands in the 2986 cm"1 region. The coupling to the bath states shows J-dependence and most interestingly, dramatically different coupling behavior between the symmetric and asymmetric tunneling puckering states.…”

Section: Discussionmentioning

confidence: 99%

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High resolution infrared spectroscopy of cyclobutane: A study of vibrational mode coupling involving large amplitude, low frequency modes

Miller

Philips

1994

The Journal of Chemical Physics

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The high resolution IR spectrum of cyclobutane in a supersonic molecular beam was obtained for the region of 2981 to 2991 cm-1. The spectrum reveals four overlapping bands suggestive of vibrational mode coupling in the C-H stretching region. Ground -state combination differences demonstrate that these bands__ Ac_:e io For originate from 2 different ground states, the symmetric and INT IS CF-., asymmetric ring puckering states. Evidence of vibrational mode, ' coupling is present in all four bands. The coupling depends on' J both J and the symmetry of the puckering state. A model:. coupling scheme involving two qualitatively different types of y couplings is developed to explain the observed spectrum.. -----------Symmetry restrictions and the Interaction between molecular" rotation and ring puckering qualitatively accounts for the[ dramatically different coupling behavior between the two ring/ puckering states.

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Section: Discussionsupporting

confidence: 90%

Section: Discussionmentioning

confidence: 99%

High resolution infrared spectroscopy of cyclobutane: A study of vibrational mode coupling involving large amplitude, low frequency modes

Miller

Philips

1994

The Journal of Chemical Physics

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“…155,159,160,162,163,[166][167][168][169][170][171][172][173][174][175][176][177] There is a trend of vibrational modes that are blue-shifted with correlation to ring strain in spectra of bulk cycloalkanes, which is similar to the trend observed for silane linked cycloalkanes ( Figure 6C). For four-, five-, and six-membered cycloalkanes, this stretching mode is assigned to an asymmetric C-H stretching motion on the basis of assignments made for bulk spectra, 155,159,160,162,163,[166][167][168][169][170][171][172][173][174] whereas for cylopropane, the blue-shift is so significant that the C-H stretch we observe on the silane surface is assigned as a symmetric stretch because the asymmetric stretch would occur at a frequency higher than the IR light probed in these experiments. 159,160,[175][176][177] Also notable in the silane spectra is the appearance of multiple peaks in the C-H asymmetric and symmetric stretching regions.…”

Section: Cyclic Alkanesmentioning

confidence: 56%

Pentane, Hexane, Cyclopentane, Cyclohexane, 1-Hexene, 1-Pentene,cis-2-Pentene, Cyclohexene, and Cyclopentene at Vapor/α-Alumina and Liquid/α-Alumina Interfaces Studied by Broadband Sum Frequency Generation

2009

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The molecular orientation and structure of adsorbates at oxide interfaces is driven by surface-molecule and molecule-molecule interactions and is useful for predicting reactivity and product selectivity in heterogeneous chemical reactions, including those important in catalytic processes. Using broadband vibrational sum-frequency generation spectroscopy, we probed cyclic and acyclic alkanes and olefins at buried vapor/solid and liquid/ solid interfaces of the R-alumina (0001) surface under ambient conditions. The spectroscopic signatures of the adsorbates were measured and compared with bulk phase spectra and spectra of model surfaces containing hydrocarbons covalently linked to glass slides using silane chemistry. By utilizing appropriate polarization combinations, the orientations of hydrocarbons adsorbed from the vapor were evaluated and compared to the hydrocarbon orientations at the liquid/solid interface. The data support a proposed orientation for n-alkanes and cycloalkanes at the liquid/solid interface in which the hydrocarbons lie with the planes of their carbon backbones parallel to the surface, whereas at the vapor/solid interface, the adsorbates are oriented with their carbon backbones in an orientation neither parallel nor perpendicular to the surface. The surface vibrational spectra of olefins at both types of interfaces indicate that their orientations differ from saturated counterparts, and their unique spectral signatures allow differentiation of adsorbed olefins from alkanes.

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“…6 These results indicated that both models gave qualitatively the same VCD but did differ in the order of magnitude of the predicted VCD. 'B2 The utility of such measurements is dependent on the development of theoretical models which can reliably represent the relationship between VCD spectra and molecular structure.…”

Section: Discussionmentioning

confidence: 87%

“…C02 is a particularly effective collision gas having low-lying transient negative ion states which dissociate into a slow electron and vibrationally excited C02. 8 The fragmentation pattern initially changes rapidly with C02 pressure as the electrons are thermalized. At higher C02 pressures the higher energy fragments such as M2(CO)8~disappear and the relative abun-(4) Waltz, W. L.; Hackelberg, O.; Dorfman, L. M.; Wojcicki, A. J. Am.…”

Section: Negative Ionsmentioning

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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Vibrational spectra and normal coordinate calculations for cis- and trans-1,2-dideuteriocyclobutanes

Cited by 20 publications

References 19 publications

High resolution infrared spectroscopy of cyclobutane: A study of vibrational mode coupling involving large amplitude, low frequency modes

High resolution infrared spectroscopy of cyclobutane: A study of vibrational mode coupling involving large amplitude, low frequency modes

Pentane, Hexane, Cyclopentane, Cyclohexane, 1-Hexene, 1-Pentene,cis-2-Pentene, Cyclohexene, and Cyclopentene at Vapor/α-Alumina and Liquid/α-Alumina Interfaces Studied by Broadband Sum Frequency Generation

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

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