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Volumn 315, Issue 5818, 2007, Pages 1561-1565

Conformationally controlled chemistry: Excited-state dynamics dictate ground-state reaction

Author keywords

[No Author keywords available]

Indexed keywords

CATION; HYDROGEN; PROPIONALDEHYDE;

EID: 33947369365     PISSN: 00368075     EISSN: 10959203     Source Type: Journal    
DOI: 10.1126/science.1136453     Document Type: Article
Times cited : (102)

References (33)
  • 16
    • 8444221247 scopus 로고    scopus 로고
    • D. Townsend et al., Science 306, 1158 (2004).
    • (2004) Science , vol.306 , pp. 1158
    • Townsend, D.1
  • 19
    • 33947403319 scopus 로고    scopus 로고
    • These values are given for the detected products only and do not account for the fraction that have undergone secondary decomposition
    • These values are given for the detected products only and do not account for the fraction that have undergone secondary decomposition.
  • 21
    • 33947371420 scopus 로고    scopus 로고
    • Uncertainties in quoted thermochemical values are on the order of 0.15 eV.
    • Uncertainties in quoted thermochemical values are on the order of 0.15 eV.
  • 26
    • 33947420585 scopus 로고    scopus 로고
    • We use 10 trajectory basis functions for each of the cis and gauche conformers. The initial position and momenta of these basis functions are randomly chosen from a Wigner distribution representing the vibrational ground state of the given conformer in the harmonic approximation. The 6-31G** basis set is used to represent the electronic wave function, along with the SA-CASSCF method equally weighting the lowest three doublet states
    • We use 10 trajectory basis functions for each of the cis and gauche conformers. The initial position and momenta of these basis functions are randomly chosen from a Wigner distribution representing the vibrational ground state of the given conformer in the harmonic approximation. The 6-31G** basis set is used to represent the electronic wave function, along with the SA-CASSCF method equally weighting the lowest three doublet states.
  • 30
    • 33947402024 scopus 로고    scopus 로고
    • After 100 fs of simulation time for the cis conformer, 30% of the final population has undergone hydrogen migration. For the gauche conformer, 0% undergoes hydrogen migration. We have examined 10 initial conditions for each conformer leading to more than 50 trajectory basis functions per conformer after adaptive expansion of the basis set through the spawning procedure, Many more simulations should be performed to get accurate branching ratios, but these results demonstrate the differing propensities in the two conformers
    • After 100 fs of simulation time for the cis conformer, 30% of the final population has undergone hydrogen migration. For the gauche conformer, 0% undergoes hydrogen migration. We have examined 10 initial conditions for each conformer (leading to more than 50 trajectory basis functions per conformer after adaptive expansion of the basis set through the spawning procedure). Many more simulations should be performed to get accurate branching ratios, but these results demonstrate the differing propensities in the two conformers.
  • 31
    • 33947382376 scopus 로고    scopus 로고
    • These pathways are determined by linear interpolation in internal coordinates between the structures representing the Franck-Condon point and each of the excited-state minima. The × axis is mass-weighted distance, in order to allow comparison of the two possible paths for each conformer
    • These pathways are determined by linear interpolation in internal coordinates between the structures representing the Franck-Condon point and each of the excited-state minima. The × axis is mass-weighted distance, in order to allow comparison of the two possible paths for each conformer.
  • 33
    • 33947368795 scopus 로고    scopus 로고
    • This work was supported by the NSF under award numbers CHE-04-15393 (A.G.S, and CHE-05-35640 and CHE-02-11876 T.J.M
    • This work was supported by the NSF under award numbers CHE-04-15393 (A.G.S.) and CHE-05-35640 and CHE-02-11876 (T.J.M.).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.