Thermodynamic functions for the cyclopentadienyl radical: The effect of Jahn-Teller distortion

被引:36
|
作者
Kiefer, JH [1 ]
Tranter, RS
Wang, H
Wagner, AF
机构
[1] Univ Illinois, Dept Chem Engn, Chicago, IL 60680 USA
[2] Argonne Natl Lab, Div Chem, Argonne, IL 60439 USA
[3] Univ Delaware, Dept Mech Engn, Newark, DE 19716 USA
关键词
D O I
10.1002/kin.10006
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We report CASSCF/cc-PVDZ calculations of the potential surface for the title Jahn-Teller molecule. Energies are calculated along all normal coordinates that can be affected by Jahn-Teller distortion. Both the E'(2) in-plane bend and stretch modes are found to be involved, but the bend contribution is very small and its contribution to the entropy is negligible. The in-plane stretch modes strongly dominate, affording a maximum stabilization energy of 4.73 kcal/mol. Harmonic frequencies are calculated for the other modes in the D-5h configuration, and these, are scaled in accordance with a comparison of experimental frequencies with similar calculations on cyclopentadiene. Energy levels for nuclear motion in the Jahn-Teller modes are then determined using the calculated surface, and these are combined with the scaled harmonic frequencies to obtain complete thermodynamic functions for the radical. The results are then fit to both the NASA polynomial form and a compact power series in inverse temperature for modeling applications. Because of changes in degeneracy and symmetry number. the entropy is actually lower than previous estimates. Nonetheless, the effect of the pseudorotation on the entropy is noticeable over the entire span of temperatures. This work is evidently the first to present both energy levels and thermodynamic functions for a Jahn-Teller molecule derived from a complete and consistent theoretical treatment, (C) 2001 John Wiley & Sons, Inc.
引用
收藏
页码:834 / 845
页数:12
相关论文
共 50 条
  • [1] JAHN-TELLER DISTORTION IN CYCLOPROPENYL RADICAL
    POPPINGER, D
    RADOM, L
    VINCENT, MA
    CHEMICAL PHYSICS, 1977, 23 (03) : 437 - 442
  • [2] A CASSCF study of the cyclopentadienyl radical: conical intersections and the Jahn-Teller effect
    Bearpark, MJ
    Robb, MA
    Yamamoto, N
    SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, 1999, 55 (03) : 639 - 646
  • [3] JAHN-TELLER EFFECT IN CYCLOPENTADIENYL RADICAL - DELOCALIZED VIBRONIC VALENCE ISOMERIZATION
    MEYER, R
    GRAF, F
    HA, TK
    GUNTHARD, HH
    CHEMICAL PHYSICS LETTERS, 1979, 66 (01) : 65 - 71
  • [4] JAHN-TELLER EFFECT IN CYCLOPENTADIENYL RADICAL - AN EXAMPLE OF 3 MODE-COUPLING
    PURINS, D
    FEELEY, HF
    JOURNAL OF MOLECULAR STRUCTURE, 1974, 22 (01) : 11 - 27
  • [5] The Jahn-Teller Distortion of C+60 Radical
    Teng, Q.-W.
    Wu, S.
    Shang, Z.-F.
    Feng, J.-K.
    Kao Teng Hsueh Hsiao Hua Heush Hsueh Pao/ Chemical Journal of Chinese Universities, 17 (05):
  • [6] The Jahn-Teller distortion of C-60(+) radical
    Teng, QW
    Wu, S
    Shang, ZF
    Feng, JK
    CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE, 1996, 17 (05): : 773 - 776
  • [7] Intrinsic Distortion Path in the analysis of the Jahn-Teller effect
    Zlatar, Matija
    Gruden-Pavlovic, Maja
    Schlaepfer, Carl-Wilhelm
    Daul, Claude
    JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2010, 954 (1-3): : 86 - 93
  • [8] Phonons and Jahn-Teller distortion in manganites
    Talati, Mina
    Jha, Prafulla K.
    JOURNAL OF MOLECULAR STRUCTURE, 2007, 838 (1-3) : 227 - 231
  • [9] JAHN-TELLER DISTORTION IN MAGNETIC SPINELS
    MIYAHARA, S
    JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN, 1962, 17 : 181 - &
  • [10] A POSSIBILITY OF ORTHORHOMBIC JAHN-TELLER DISTORTION
    MURAMATSU, S
    IIDA, T
    JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, 1970, 31 (10) : 2209 - +