Ab initio and Direct Quasiclassical Trajectory Study of the F + CH₄ → HF + CH₃ and F + C₂H₆ → HF + C₂H₅ Reactions

The reparametization of semiempirical Hamiltonians is an emerging method used in direct dynamics studies. The use of semiempirical Hamiltonians in direct dynamics studies diminishes the computational cost of trajectory calculations and negates the need for an analytical potential energy surface when performing reaction dynamics studies. The reparametization of semiempirical Hamiltonians increases the agreement with experiment and high level ab initio theory. We have chosen to create one set of new parameters that apply to two related reactions, F + CH₄ → HF + CH₃ and F + C₂H₆ → HF + C₂H₅. We have performed an electronic structure study for these reactions. The ab initio data obtained from the electronic structure study is then used as the reference for a reparametization of the PM3 Hamiltonian. The reparametization has improved the ab initio and PM3 reaction energy and potential energy surface scan agreement. This new set of parameters for PM3 (SRP-PM3) is used to perform a direct quasiclassical trajectory study of the reactions. The vibrational and rotational HF distributions calculated using SRP-PM3 are compared with experiments. We have observed an improvement in the agreement with experimental vibrational distributions but have seen no change in the rotational distributions.

Name thesis:degree_name

Master of Science

Level thesis:degree_level

masters

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2007

Author dc:creator

• Weiss, Paula

Chair dc:contributor.committeechair

• Troya, Diego

Committee members dc:contributor.committeemember

• Crawford, T. Daniel
• Gandour, Richard D.
• Morris, John R.
• Valeyev, Eduard Faritovich

• potential energy surface
• direct dynamics
• specific reaction parameter semiempirical Hamilton
• quasiclassical trajectory study

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

etd-10092007-111213

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/35340