A classical dynamics study of the anisotropic interactions in NNO–Ar and NNO–Kr systems: Comparison with transport and relaxation data

Horst, Marc A. ter; Jameson, Cynthia J.

doi:10.1063/1.477719

Cited by 2 publications

References 44 publications

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Molecular reorientation of CD₄in gas‐phase mixtures

Horst

Jameson

2006

Magnetic Reson in Chemistry

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Spin-lattice relaxation times were measured for the deuterons in CD(4) in pure gas and in mixtures with the following buffer gases: Ar, Kr, Xe, HCl, N(2), CO, CO(2), CF(4), and SF(6). Effective collision cross sections sigma(theta, 2) for the molecular reorientation of CD(4) in collisions with these ten molecules are obtained as a function of temperature. These cross sections are compared with the corresponding cross sections sigma(J) obtained from (1)H spin-rotation relaxation in mixtures of CH(4) with the same set of buffer gases. Various classical reorientation models typically applied in liquids predict different ratios of the reduced correlation times for the reorientation of spherical tops. The Langevin model comes closest to predicting the magnitude of the sigma(theta, 2)/sigma(J) ratio that we obtain for CD(4).

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Molecular reorientation of CD₄in gas‐phase mixtures

Horst

Jameson

2006

Magnetic Reson in Chemistry

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Fundamental Intramolecular and Intermolecular Information from NMR in the Gas Phase

Jameson

2016

Gas Phase NMR

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Since theories on the behavior of dilute gases are in an advanced stage compared to condensed phases and complex materials, gas phase NMR measurements offer opportunities unique to the gas phase for fundamental understanding of the dependence of NMR quantities (shielding, J coupling) on the internal coordinates of the molecule (the property surfaces that mathematically describe how these molecular electronic properties change while the molecule carries out vibrational motions). The virial expansion is valid in the dilute gas, so that observations in the linear-density regime uniquely permit the determination of the linear-density dependence of NMR quantities, the second virial property coefficients that can be calculated in closed form by direct integration, if the intermolecular potential energy surface (PES) is known. Precise measurements afforded by NMR provide tested general theoretical treatments of intermolecular effects and intramolecular averaging that apply also to other molecular electronic properties. Spin–lattice relaxation times in the linear-density regime also provide a direct connection to the intermolecular PES; they can be calculated in terms of two well-defined cross-sections involving changes in molecular orientation and molecular rotational angular momentum sensitive to the anisotropy of the PES by well-established theory. Finally, observations of chemical exchange processes in gas phase NMR provide tests of kinetic theories for molecular rearrangements (RRKM) and transition state theory, and so provide tests of calculated transition states, reaction surfaces, and activation thermodynamic quantities such as ΔG⧧, ΔH⧧, ΔS⧧.

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A classical dynamics study of the anisotropic interactions in NNO–Ar and NNO–Kr systems: Comparison with transport and relaxation data

Cited by 2 publications

References 44 publications

Molecular reorientation of CD₄in gas‐phase mixtures

Molecular reorientation of CD₄in gas‐phase mixtures

Fundamental Intramolecular and Intermolecular Information from NMR in the Gas Phase

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A classical dynamics study of the anisotropic interactions in NNO–Ar and NNO–Kr systems: Comparison with transport and relaxation data

Cited by 2 publications

References 44 publications

Molecular reorientation of CD4in gas‐phase mixtures

Molecular reorientation of CD4in gas‐phase mixtures

Fundamental Intramolecular and Intermolecular Information from NMR in the Gas Phase

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Molecular reorientation of CD₄in gas‐phase mixtures

Molecular reorientation of CD₄in gas‐phase mixtures