Disentangling long trajectory contributions in two-colour High Harmonic Generation
Landsman, Alexandra S.
- Journal Article
Rights / licenseCreative Commons Attribution 4.0 International
Born-Oppenheimer molecular dynamics trajectory calculations at the HCTH147/6-31G** level of theory simulate the dissociation dynamics of photolytically excited 1,1-difluoroethyl radicals. EOMCCSD/AUG-cc-pVDZ calculations show that an excitation energy of 94.82 kcal/mol is necessary to initiate photodissociation reactions. In contrast to photodissociation dynamics of ethyl radicals where a large discrepancy between actual dissociation rates and rates that are predicted by statistical rate theories, we find reaction rates of 5.1 × 1011 s−1 for the dissociation of an H atom, which is in perfect accord with what is predicted by Rice-Ramsperger-Kassel-Marcus (RRKM) calculations and there is no indication of any nonstatistical effects. However, our trajectory calculations show a much larger fraction of C–C bond breakage reaction of 56% occurring than that expected by RRKM (only 16%) Show more
Journal / seriesApplied Sciences
Pages / Article No.
SubjectClassical trajectory Monte Carlo simulation; High harmonic spectroscopy; Strong-field ionisation; Two-colour high harmonic generation
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