메뉴 건너뛰기




Volumn 104, Issue 51, 2000, Pages 11853-11863

Vibrational Stark effects of nitriles. I. Methods and experimental results

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUNDS; ELECTRIC FIELDS; FOURIER TRANSFORM INFRARED SPECTROSCOPY; GLASS; POLARIZATION;

EID: 0034499168     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp002242r     Document Type: Article
Times cited : (241)

References (42)
  • 16
    • 0042599829 scopus 로고
    • Acetonitrile-the structure of the liquid and solid phases and the nature of the liquid-solid-phase transition
    • Buckingham, A. D., Lippert, E., Bratos, S., Eds.; John Wiley & Sons: New York
    • Michel, H.; Lippert, E. Acetonitrile-The structure of the liquid and solid phases and the nature of the liquid-solid-phase transition. In Organic Liquids. Structure, dynamics, and chemical properties; Buckingham, A. D., Lippert, E., Bratos, S., Eds.; John Wiley & Sons: New York, 1978; p 293.
    • (1978) Organic Liquids. Structure, Dynamics, and Chemical Properties , pp. 293
    • Michel, H.1    Lippert, E.2
  • 29
    • 0342449369 scopus 로고    scopus 로고
    • note
    • Three factors appear to improve the signal-to-noise for rapid-scan methods relative to step-scan methods: (i) it is not necessary to wait for a lock-in to settle after each mirror step, (ii) multiplexing of signal frequencies is used, and (iii) interferogram oversampling requires no additional time. This is discussed more fully in Andrews, S. S.; Boxer, S. G. In preparation.
  • 30
    • 0343318836 scopus 로고    scopus 로고
    • note
    • Early experiments were performed in a miniature Joule-Thompson refrigerator (MMR Technologies) operating at 80 K, but we found significant sample orientation in an electric field, leading to the development of the immersion cryostat. Poling may not be a problem for AC electric fields.
  • 31
    • 0342449368 scopus 로고    scopus 로고
    • note
    • Data fitting was done with Macintosh software created for this purpose. The software and C language source code are available upon request.
  • 32
    • 0342449367 scopus 로고    scopus 로고
    • note
    • The parameters of a modified Voigt are: peak height, frequency, full width at half-maximum, and the Gaussian:Lorentzian ratio. These parameters are adjusted only to obtain a best fit to the absorption spectrum, and are not considered to have any physical meaning.
  • 33
    • 0342449366 scopus 로고    scopus 로고
    • note
    • χ would be corrected to be 13% too small under the one-dimensional assumptions, contributing to a 7% error in the calculation of |Δμ|.
  • 36
    • 25344474688 scopus 로고
    • Linear coupling between two modes results in redefined normal modes and a separation of the absorption peaks, whereas nonlinear coupling gives absorption between the peaks, and is responsible for Fermi resonance. The excess absorption is analogous to the coalescence seen in NMR spectra of dynamic systems (see e.g. Gasparro, F. P.; Kolodny, N. H. J. Chem. Educ. 1977, 54, 258-261).
    • (1977) J. Chem. Educ. , vol.54 , pp. 258-261
    • Gasparro, F.P.1    Kolodny, N.H.2
  • 37
    • 0012918413 scopus 로고
    • Atomic and molecular polarizabilities
    • Lide, D. R., Ed.; CRC Press: Boca Raton, FL
    • Miller, T. M. Atomic and molecular polarizabilities. In Handbook of Chemistry and Physics, 71st ed.; Lide, D. R., Ed.; CRC Press: Boca Raton, FL, 1990; p 10.
    • (1990) Handbook of Chemistry and Physics, 71st Ed. , pp. 10
    • Miller, T.M.1
  • 38
    • 0004230584 scopus 로고
    • Worth Publishers: New York
    • The transition state enthalpy is expected to be about 16 kJ/mol, from butane data (see e.g., Kemp, D. S.; Vellaccio, F. Organic Chemistry; Worth Publishers: New York, 1980; p. 472), implying an interconversion rate below 1 ms down to the 100 K glass transition temperature, which is fast compared to the freezing rate. Thus, low-temperature population ratios were computed for 100 K, with the assumption that the sample is at equilibrium before freezing and immobilized thereafter. Boltzmann population calculations use an enthalpy difference between anti and gauche conformations of 2.8 kJ/mol, a value found by AM1 calculations for the relevent nitriles.
    • (1980) Organic Chemistry , pp. 472
    • Kemp, D.S.1    Vellaccio, F.2
  • 40
    • 85050425869 scopus 로고
    • Cyanogen was synthesized by an adaptation of a method from: Janz, George J. Inorg. Synth. 1957, 5, 43-48.
    • (1957) Inorg. Synth. , vol.5 , pp. 43-48
    • Janz, G.J.1
  • 41
    • 0004255576 scopus 로고
    • University Science Books: Sausalito, CA
    • McQuarrie, D. A. Quantum Chemistry; University Science Books: Sausalito, CA, 1983.
    • (1983) Quantum Chemistry
    • McQuarrie, D.A.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.