Abstract
▪ Abstract Modern ultrafast spectroscopic techniques provide new opportunities to study chemical reaction dynamics in liquids and hold the possibility of obtaining much of the same detailed information available in gases. Vibrational energy transfer studies are the most advanced of the investigations and demonstrate that it is possible to observe state-specific pathways of energy flow within a vibrationally excited molecule (intramolecular vibrational relaxation) and into the surrounding solvent molecules (intermolecular energy transfer). Energy transfer in liquids and gases share many common aspects, but the presence of the solvent also alters the relaxation in both obvious and subtle ways. Photodissociation is amenable to similarly detailed study in liquids, and there are informative new measurements. Bimolecular reactions have received the least attention in state-resolved measurements in liquids, but the means to carry them much further now exist. Studying photodissociation and bimolecular reaction of molecules prepared with initial vibrational excitation in liquids is a realistic, but challenging, goal.
Keywords
Vibrational energy relaxationIntermolecular forceChemical physicsIntramolecular forceExcited statePhotodissociationRelaxation (psychology)MoleculeChemical reactionSolventChemistryExcitationVibrational energySolvent effectsAtomic physicsComputational chemistryPhotochemistryPhysicsOrganic chemistry
Affiliated Institutions
Related Publications
Femtosecond Stimulated Raman Exposes the Role of Vibrational Coherence in Condensed-Phase Photoreactivity
Femtosecond spectroscopy has revealed coherent wave packet motion time and time again, but the question as to whether these coherences are necessary for reactivity or merely a c...
Ultrafast Electron Transfer Dynamics from Molecular Adsorbates to Semiconductor Nanocrystalline Thin Films
Interfacial electron transfer (ET) between semiconductor nanomaterials and molecular adsorbates is an important fundamental process that is relevant to applications of these mat...
The Statistical Mechanical Theory of Transport Processes I. General Theory
Outlines are sketched for a general statistical mechanical theory of transport processes; e.g., diffusion, heat transfer, fluid flow, and response to time-dependent external for...
Theoretical Solar-to-Electrical Energy-Conversion Efficiencies of Perylene−Porphyrin Light-Harvesting Arrays
The efficiencies of organic solar cells that incorporate light-harvesting arrays of organic pigments were calculated under 1 sun of air mass 1.5 solar irradiation. In one set of...
On the Analytical Mechanics of Chemical Reactions. Quantum Mechanics of Linear Collisions
The analytical quantum mechanics of chemically reactive linear collisions is treated in the vibrationally near-adiabatic approximation. The ``reaction coordinate'' in this appro...
Publication Info
- Year
- 2005
- Type
- article
- Volume
- 57
- Issue
- 1
- Pages
- 273-302
- Citations
- 136
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
136
OpenAlex
Cite This
Christopher G. Elles,
F. Fleming Crim
(2005).
CONNECTING CHEMICAL DYNAMICS IN GASES AND LIQUIDS.
Annual Review of Physical Chemistry
, 57
(1)
, 273-302.
https://doi.org/10.1146/annurev.physchem.57.032905.104538
Identifiers
- DOI
- 10.1146/annurev.physchem.57.032905.104538