Rotational heating during IR multiphoton excitation

doi:10.1016/0009-2614(79)85163-5

Chemical Physics Letters

Volume 67, Issues 2–3, 15 November 1979, Pages 284-288

https://doi.org/10.1016/0009-2614(79)85163-5 Get rights and content

Abstract

It is shown that significant rotational heating can accompany the infrared multiphoton excitation of polyatomic molecules. The dynamical effects of this heating on dissociation products are discussed. Results of a simple model are displayed.

References (11)

CantrellC.D. et al.
Opt. Commun.
(1976)
FussW.
Chem. Phys.
(1979)
AmbartzumianR.V. et al.
JETP Letters
(1975)
IsenorN.R. et al.
Appl. Phys. Letters
(1971)
AmbartzumianR.V. et al.

There are more references available in the full text version of this article.

Cited by (8)

Collisional deactivation of CF <inf>3</inf> I - a molecular dynamics simulation
1999, Chemical Physics
The detailed mechanisms of ro-vibrational energy transfer in collisions between CF₃I and argon or propane are investigated. Molecular dynamics simulations of collisions between a reactant CF₃I molecule at energies from 50 to 200 kJ/mol with medium argon or propane at selected initial temperatures are interpreted in terms of ergodic collision limits. The intramolecular potential used for CF₃I is a Morse-stretch/harmonic-bend type function with parameters fitted to equilibrium structure, normal mode frequencies and dissociation energies. Simple generic Buckingham type pair-potentials are used for intermolecular atom–atom interactions. Energy transfer is related to (i) geometry of collision, (ii) impact parameter, (iii) number of atom–atom encounters, (iv) average dynamical hardness of interaction at atom–atom collisions, (v) number of minima in the center of mass separation and (vi) lifetime of the collisional complex. The energy transfer in our molecular dynamics calculations is compared with experimental results for the same colliders. The observed trends are interpreted in terms of detailed collisional mechanisms. Our results highlight the importance of rotational excitation and the repulsive part of the intermolecular potential.
Trajectory study of energy partition in CF<inf>3</inf>CN → CF<inf>3</inf> + CN dissociation dynamics
1986, Chemical Physics
The classical trajectory method has been used to study the internal dynamics and unimolecular dissociation of CF₃CN at energies consistent with infrared multiphoton excitation conditions. A model potential energy function consisting of Morse stretches and attenuated bending terms is used in the trajectory study. At an excitation energy of 150 kcal/mol the CN K. The vibrational and rotational distributions are approximately Boltzmann. This energy partitioning is in good agreement with recent experimental results. The trajectory unimolecular rate constants and lifetime distributions for CF₃CN dissociation are consistent with intrinsic RRKM behaviour.
Extension of total angular momentum representation in energy space
1985, Chemical Physics Letters
The importance of spectroscopy for infrared multiphoton excitation
1981, Progress in Quantum Electronics
Collisionless IR multiphoton absorption in propynal
1980, Chemical Physics Letters
Wavelength dependence of rovibronic populations of propynal vibrationally excited under collisionless conditions and probed by laser-induced fluorescence, is compared with energy deposition measurements determined photoacoustically. The data show that under conditions of multiphoton absorption, excitation of the lower vibrational manifold is wavelength dependent and not well correlated with the total energy deposited.
Nascent PO(X <sup>2</sup>Π) E,V,R,T excitations from collision-free IR laser photolysis: Specificity toward the PO(X <sup>2</sup>Π<inf>1/2</inf>) spin-orbit state
1985, The Journal of Chemical Physics

View all citing articles on Scopus

View full text

Rotational heating during IR multiphoton excitation

Abstract

Opt. Commun.

Chem. Phys.

JETP Letters

Appl. Phys. Letters