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Volumn 125, Issue 14, 2003, Pages 4368-4375

Continuous symmetry numbers and entropy

Author keywords

[No Author keywords available]

Indexed keywords

ENTROPY CHANGE;

EID: 0037427248     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja020619w     Document Type: Article
Times cited : (26)

References (60)
  • 14
    • 33344476386 scopus 로고
    • The symmetry numbers were introduced in the rotational partition function by: Ehnrenfest, P.; Trkal, V. Proc. Sect. Sci., Amsterdam 1920, 23, 162. See also: Mayer, J. E.; Brunauer, S.; Mayer, M. G. J. Am. Chem. Soc. 1933, 55, 37.
    • (1920) Proc. Sect. Sci., Amsterdam , vol.23 , pp. 162
    • Ehnrenfest, P.1    Trkal, V.2
  • 15
    • 0242528033 scopus 로고
    • The symmetry numbers were introduced in the rotational partition function by: Ehnrenfest, P.; Trkal, V. Proc. Sect. Sci., Amsterdam 1920, 23, 162. See also: Mayer, J. E.; Brunauer, S.; Mayer, M. G. J. Am. Chem. Soc. 1933, 55, 37.
    • (1933) J. Am. Chem. Soc. , vol.55 , pp. 37
    • Mayer, J.E.1    Brunauer, S.2    Mayer, M.G.3
  • 18
    • 0242612773 scopus 로고    scopus 로고
    • note
    • 3h example, consider a (hypothetical) reaction inducing this change in symmetry, that is, an isomerization or a trisubstituion reaction of benzene (reactant A). The change in rotational entropy due to the change in the symmetry numbers is R ln(6/12) = -5.76 J/(K·mol). That is, in eq V, the entropic symmetry term adds (twice negative) to the total rotational entropy, reflecting the conversion to a lower symmetry (A to B).
  • 20
    • 0001461441 scopus 로고
    • The first report recognizing the difficulties with the symmetry numbers in systems that change the symmetry is probably: Pitzer, K. S. J. Chem. Phys. 1939, 7, 251. See also: Pitzer, K. S., Ed. Molecular Structure and Statistical Thermodynamics. Selected Papers of K. S. Pitzer; World Scientific: Singapore, 1993; pp 189 and a comment on p 194.
    • (1939) J. Chem. Phys. , vol.7 , pp. 251
    • Pitzer, K.S.1
  • 21
    • 0001461441 scopus 로고
    • World Scientific: Singapore; and a comment on p 194
    • The first report recognizing the difficulties with the symmetry numbers in systems that change the symmetry is probably: Pitzer, K. S. J. Chem. Phys. 1939, 7, 251. See also: Pitzer, K. S., Ed. Molecular Structure and Statistical Thermodynamics. Selected Papers of K. S. Pitzer; World Scientific: Singapore, 1993; pp 189 and a comment on p 194.
    • (1993) Molecular Structure and Statistical Thermodynamics. Selected Papers of K. S. Pitzer , pp. 189
    • Pitzer, K.S.1
  • 33
    • 0003851335 scopus 로고
    • W. H. Freeman and Co.: San Francisco
    • Wall, F. T. Chemical Thermodynamics; W. H. Freeman and Co.: San Francisco, 1958; p 271.
    • (1958) Chemical Thermodynamics , pp. 271
    • Wall, F.T.1
  • 42
    • 0242444528 scopus 로고    scopus 로고
    • note
    • 1 does not change the basic arguments of this section.
  • 52
    • 0242696893 scopus 로고    scopus 로고
    • note
    • The structure for symmetric proton position was taken as the average of those determined by X-ray diffraction in refs 50 and 51. In the case of the asymmetric position, the structures of refs 52 and 53 were averaged. In all cases, the distances N-H-N computed by ab initio quantum chemical methods were taken into account as reported in ref 54.
  • 58
    • 0242444526 scopus 로고    scopus 로고
    • note
    • Data taken from ref 56; the molecular structures of the anions are after geometry optimization, using DFT calculations; the distortions were attributed there to the Jahn-Teller effect.
  • 60
    • 0242696892 scopus 로고    scopus 로고
    • note
    • 56


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.