Vibrational relaxation of diatomic molecules in liquids

Harris, Charles B.; Smith, David Eugene; Russell, Daniel

doi:10.1021/cr00101a003

Cited by 154 publications

(63 citation statements)

References 13 publications

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“…The results of this work could be useful in areas where P(f ) is a relevant quantity in developing statistical mechanical descriptions of certain processes, such as vibrational dephasing of diatomic molecules in a solvent, 20,21 where the large force part of the force spectrum can dominate the process. It could be useful in helping to provide a more fundamental background for understanding force distributions in granular and suspension media, as we have alluded to at various places in this work.…”

Section: Discussionmentioning

confidence: 99%

Pair force distributions in simple fluids

Brańka

Heyes

Rickayzen

2011

The Journal of Chemical Physics

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Analytic expressions are derived for the frequency distribution, P(f), of pair forces, f, and those of their α-Cartesian component, f(α), or P(f(α)), for some typical model simple fluids, expressed in terms of the radial distribution function and known constants. For strongly repulsive inverse power (IP), exponential and Yukawa purely repulsive potentials, P(f) diverges at the origin approximately as ∼f(-1), but with different limiting analytic forms. P(f(α)) is also shown to diverge as ∼f(-1) as f → 0 for the IP fluid. For the Lennard-Jones potential fluid, P(f) is finite for all f ≥ 0 but has two singularities for negative f, corresponding to the zero force limit (i.e., f → 0(-)) and the point of inflection in the potential. The corresponding component force distribution is singular as f(α) → 0 from both positive and negative force sides. The large force limit of P(f), which originates from the close neighbor interactions, is nearly exponential for the IP and LJ fluids, as is also found for granular materials. A more complete picture of force distributions in off-lattice particulate systems as a function of force law and state point (particularly the extent of "thermalization" of the particles) is provided.

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Section: Discussionmentioning

confidence: 99%

Pair force distributions in simple fluids

Brańka

Heyes

Rickayzen

2011

The Journal of Chemical Physics

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“…The study and modeling of vibrational relaxation [63] indicate molecular collisions occur on the order of picoseconds in liquids. The rotational correlation times derived from the NMR relaxation measurements are on the order of 100 ps, in good agreement with "the rotational relaxation of solute particles of a few hundred cubic angstroms in volume [that] occurs on timescales of tens to hundreds of picoseconds," as measured in ultrafast laser studies [64].…”

Section: Relaxation Of Hgcl 2 In Dmso Solutionsmentioning

confidence: 99%

Revisiting HgCl2: A solution- and solid-state 199Hg NMR and ZORA–DFT computational study

Taylor

Carver

Larsen

et al. 2009

Journal of Molecular Structure

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The 199 Hg chemical-shift tensor of solid HgCl 2 was determined from spectra of polycrystalline materials, using static and magic-angle spinning (MAS) techniques at multiple spinning frequencies and field strengths. The chemical-shift tensor of solid HgCl 2 is axially symmetric (η = 0) within experimental error. The 199 Hg chemical-shift anisotropy (CSA) of HgCl 2 in a frozen solution in dimethylsulfoxide (DMSO) is significantly smaller than that of the solid, implying that the local electronic structure in the solid is different from that of the material in solution. The experimental chemicalshift results (solution and solid-state) are compared with those predicted by density functional theory (DFT) calculations using the zeroth-order regular approximation (ZORA) to account for relativistic effects.199 Hg spin-lattice relaxation of HgCl 2 dissolved in DMSO is dominated by a CSA mechanism, but a second contribution to relaxation arises from ligand exchange. Relaxation in the solid state is independent of temperature, suggesting relaxation by paramagnetic impurities or defects.

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“…In addition, coupling to the solvent can strongly influence the vibrational and electronic relaxation of the solute, and thereby influence the reaction pathway. The I 2 photodissociation reaction is a simple model system for understanding molecular dynamics in solution, and there have been extensive theoretical and time-resolved experimental studies [71,[84][85][86][87][88]. Measurements with femtosecond optical pulses indicate that vibrational coherence is maintained as photo-excited molecules in solution undergo curve-crossing to a dissociative state within a few hundred femtoseconds [71].…”

Section: Solvent-solute Structural Dynamicsmentioning

confidence: 99%