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Volumn 117, Issue 19, 2002, Pages 8855-8866

Femtosecond electron ejection in liquid acetonitrile: Evidence for cavity electrons and solvent anions

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER; COMPUTER SIMULATION; ELECTRON ENERGY LEVELS; LASER PULSES; MOLECULAR DYNAMICS; NEGATIVE IONS; PHOTOIONIZATION; PROBES; PUMPING (LASER); QUANTUM THEORY; RADIOLYSIS; SPECTROSCOPY;

EID: 0037113099     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1513152     Document Type: Article
Times cited : (60)

References (89)
  • 34
    • 0012016894 scopus 로고    scopus 로고
    • note
    • - did not interfere with the much larger signlas from iodide.
  • 38
    • 0012045504 scopus 로고    scopus 로고
    • note
    • All calculations were done using GAUSSIAN 98, Revision A7 (Ref. 83). Diffuse basis functions were not used in these calculations, since these functions do a poor job of predicting negative electron affinities (Refs. 42, 84, 85) Basis sets with diffuse functions tend to converge to the dipolebound anion states, when these states exist (Ref. 86). The vertical electron affinity (VEA) for each species of interest is given by the energy of the geometry optimized neutral minus the energy of the anion at the same geometry. Adiabatic electron affinities (AEAs) were calculated by separately optimizing the geometry of both the neutral and its corresponding anion. Since uncertainties in the calculated electron affinities are expected to be at least several tenths of an eV with the basis sets used zero point energy corrections were not applied. AEAs in liquid acetonitrile were estimated by calculating energies with the polarizable continuum model (option PCM to the SCRF Gaussian keyword) built into the GAUSSIAN 98 package. For these calculations, the dielectric constant of acetonitrile was used at room temperature. Energies were computed in this case using gas-phase geometries, since the more expensive procedure of geometry optimization within the continuum solvation model did not result in significant energy differences. All geometry optimizations were performed without any symmetry constraints.
  • 54
    • 0012050101 scopus 로고    scopus 로고
    • note
    • max = 260 nm (Ref. 87)].
  • 55
    • 0012053182 scopus 로고    scopus 로고
    • note
    • - shows essentially no absorption (Ref. 36).
  • 56
    • 0012016771 scopus 로고    scopus 로고
    • note
    • -1. This is considerably above the high-energy limit of our detection windows, indicating that cyanide ion does not contribute to our observed signals.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.