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Vibrations and Thermodynamics of Clusters of Polycyclic Aromatic Hydrocarbon Molecules: The Role of Internal Modes
- Source :
- Journal of Physical Chemistry A, Journal of Physical Chemistry A, American Chemical Society, 2007, 111 (16), pp.2999-3009. ⟨10.1021/jp068821z⟩
- Publication Year :
- 2007
- Publisher :
- American Chemical Society (ACS), 2007.
-
Abstract
- The vibrational spectra of clusters of coronene molecules are theoretically calculated using a mixed quantum/ classical scheme, each molecule being described by a tight-binding Hamiltonian, the intermolecular forces being provided by explicit Lennard-Jones and point charge sites. The normal modes of vibrations are shown to exhibit significant variations upon clustering. In particular, for large clusters intra- and intermolecular modes tend to mix and fill the mid-infrared range. We also calculate the heat capacity of the (C 24 H 12 ) 8 cluster as a function of temperature, emphasizing the isomerizations that take place during melting. Quantum delocalization effects, as obtained from the Pitzer-Gwinn semiclassical approximation, are important enough to wash out all signatures of the structural transitions on the caloric curve. On the basis of a simple two-state model we estimate that clusters containing about 300 molecules are required for melting to be detected on the caloric curve.
- Subjects :
- 010304 chemical physics
Chemistry
Intermolecular force
Semiclassical physics
010402 general chemistry
01 natural sciences
Heat capacity
Coronene
0104 chemical sciences
symbols.namesake
chemistry.chemical_compound
Delocalized electron
Normal mode
Chemical physics
0103 physical sciences
Physics::Atomic and Molecular Clusters
symbols
Cluster (physics)
Physics::Chemical Physics
Physical and Theoretical Chemistry
Atomic physics
Hamiltonian (quantum mechanics)
ComputingMilieux_MISCELLANEOUS
Subjects
Details
- ISSN :
- 15205215 and 10895639
- Volume :
- 111
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry A
- Accession number :
- edsair.doi.dedup.....53af46cdc6ca62c45e2314b5435535ed