Infrared Spectra and Intermolecular Potentials of Matrix-Isolated Nitromethane and Nitromethane-<i>d</i>3

Verderame, Frank D.; Lannon, Joseph A.; Harris, L. E.; Thomas, W. G.; Lucia, E. A.

doi:10.1063/1.1677591

Cited by 51 publications

(12 citation statements)

References 15 publications

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“…It is widely accepted that there are significant intermolecular interactions in liquid nitromethane, particularly at higher pressures. ,,,− To better characterize them, our NVT simulation included a determination of the autocorrelation functions for a single molecule and collective dipole moments ), as are accordingly the corresponding reorientation (or relaxation) times τ S and τ C , estimated (from the slopes of ln C vs t ) to be 9 and 7 ps, respectively.…”

Section: Discussionmentioning

confidence: 99%

Molecular Dynamics Simulations of Liquid Nitromethane

1999

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A potential energy function with harmonic intramolecular and Lennard-Jones plus Coulombic intermolecular terms was tested in molecular dynamics simulations of liquid nitromethane. Parameter values were adjusted iteratively until satisfactory agreement with density functional pair calculations and experimental data was achieved. The properties computed using the NVT and NPT ensembles were the heat of vaporization, dielectric constant, self-diffusion coefficient, density, heat capacity at constant pressure, pair correlation functions, single molecule and collective dipole moment reorientation times, the vibrational spectrum, and the effect of increasing pressure upon the C−N stretching frequency. Overall, the results were in reasonable accord with experimental results, the greatest discrepancy being for the dielectric constant. It was concluded, on the basis of the reorientation times and the calculated molecular surface electrostatic potential, that the intermolecular interactions in liquid nitromethane at 1 atm are not highly directional and site-specific.

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Section: Discussionmentioning

confidence: 99%

Molecular Dynamics Simulations of Liquid Nitromethane

1999

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“…A number of studies on the vibrational spectra of nitromethane at ambient temperature and pressure exist in the literature. [29][30][31][32] Symmetry assignments of the different Raman and far-infrared mode assignments have been summarized. [29][30][31] In the C^point group, the 15 vibrational modes are divided into 5A], 4Bt, SBa, and IA2 symmetries.…”

Section: Summary Of Previous Workmentioning

confidence: 99%

Time-Resolved Raman Measurements in Nitromethane Shocked to 140 kbar

Pangilinan¹,

Gupta²

1994

J. Phys. Chem.

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Time-resolved Raman spectra of nitromethane shocked to 140 kbar peak pressure using step wave loading have been obtained. The CN stretch (917 cm-l), CH3 stretch (2968 cm-l), and the NO2 stretch/CH3 bend (1400/ 1377 cm-1) vibrations are all observed to harden when peak pressure is attained in the liquid samples. The spectra obtained show no frequency softening up to 400 ns after peak pressure is reached in the material. Upon unloading from 140 kbar, the CN stretch vibration reverts back, showing no signs of an irreversible change. W e also observe that the vibrational frequencies increase nonlinearly with peak pressure, with the CH3 stretching mode exhibiting the largest increase. The observed frequency hardening and broadening are suggestive of strong intermolecular interactions at these shock pressures. Implications of these observations with regard to attaining a precursor state for shock-induced chemical reactions are discussed.

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“…Earlier spectroscopic works on nitromethane investigated the microwave − spectra as well as low-resolution IR and Raman spectra in the region of the fundamentals − and the overtones. , In this study, the dynamics of nitromethane in the first C−H stretching overtone region (6047−6055 cm -1 ) was investigated at very high resolution (≈6 MHz) using a molecular beam laser spectrometer. The purpose was 2-fold.…”

Section: Introductionmentioning

confidence: 99%

Molecular Beam Infrared Spectrum of Nitromethane in the Region of the First C−H Stretching Overtone

Halonen¹,

Halonen²,

Callegari³

et al. 1998

J. Phys. Chem. A

103

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The infrared spectrum of the first C−H stretching overtone of nitromethane (CH3NO2) was measured in the wavenumber region 6047−6055 cm-1 with a resolution of 5 MHz using a molecular beam laser spectrometer equipped with bolometric optothermal detection and a power build-up cavity. The assignment of the spectrum was made using ground-state combination differences and an asymmetric rotor energy level simulation program. The following parameters were obtained for the m = 0 upper state: ν0 = 6050.1378(24) cm-1, A = 0.55399(84) cm-1, B = 0.2936(15) cm-1, C = 0.2567(13) cm-1. The intramolecular vibrational energy redistribution (IVR) rate of the C−H stretch was calculated from the spectrum. The IVR rate of the different J K a K c levels in the spectrum ranged from 170 to 300 ps, comparable to the rate measured for methyl C−H stretching overtones in molecules of similar size (CH3SiH3 and CH3CD3).

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Infrared Spectra and Intermolecular Potentials of Matrix-Isolated Nitromethane and Nitromethane-d3

Cited by 51 publications

References 15 publications

Molecular Dynamics Simulations of Liquid Nitromethane

Molecular Dynamics Simulations of Liquid Nitromethane

Time-Resolved Raman Measurements in Nitromethane Shocked to 140 kbar

Molecular Beam Infrared Spectrum of Nitromethane in the Region of the First C−H Stretching Overtone

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