The rotational spectrum of the complex 2,5-dihydrofuran center dot center dot center dot HBr and the non-linearity of the O center dot center dot center dot H-Br hydrogen bond

被引:6
作者
Cooke, SA [1 ]
Corlett, GK [1 ]
Evans, CM [1 ]
Legon, AC [1 ]
机构
[1] UNIV EXETER, DEPT CHEM, EXETER EX4 4QD, DEVON, ENGLAND
来源
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS | 1997年 / 93卷 / 17期
关键词
D O I
10.1039/a702576i
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
a-Type and c-type ground-state rotational transitions belonging to the two isotopomers C4H6O...(HBr)-Br-79 and C4H6O...(HBr)-Br-81 of a hydrogen-bonded complex formed by 2,5-dihydrofuran with hydrogen bromide have been measured by using a pulsed-nozzle, Fourier-transform microwave spectrometer. Spectral analysis leads to the rotational constants A(o), B-o, C-o, the centrifugal distortion constants Delta(J) Delta(JK)Delta(K), delta(J), the complete Br-nuclear quadrupole coupling tensor chi alpha beta (alpha,beta = a, b, c), and the spin-rotation coupling constant 1/2(M-bb + M-cc) in each case. A detailed interpretation of the spectroscopic constants establishes that the complex has C-s symmetry, with the HBr subunit lying in the molecular symmetry plane and forming a hydrogen bond to the oxygen atom of 2,5-dihydrofuran. The angle between the O...H internuclear line and the C, axis of 2,5-dihydrofuran takes the value phi = 122.5(3)degrees while the O...H-Br nuclei are found to deviate by theta = 10.2(1)degrees from collinearity. The distance r(O...H) = 1.799(5) Angstrom. The quantities r(O...H), phi and theta are compared for the series of complexes (CH2)(2)O...HX andC(4)H(6)O...HX (X = Cl or Br) and their variation rationalized on the basis of a simple model of the hydrogen bond.
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页码:2973 / 2976
页数:4
相关论文
共 20 条
[1]   FABRY-PEROT CAVITY PULSED FOURIER-TRANSFORM MICROWAVE SPECTROMETER WITH A PULSED NOZZLE PARTICLE SOURCE [J].
BALLE, TJ ;
FLYGARE, WH .
REVIEW OF SCIENTIFIC INSTRUMENTS, 1981, 52 (01) :33-45
[2]   PRE-REACTIVE INTERMEDIATES IN MIXTURES OF HYDROCARBONS WITH CHLORINE MONOFLUORIDE - CHARACTERIZATION OF ETHYNE-CENTER-DOT-CENTER-DOT-CENTER-DOT-CLF AND ETHENE-CENTER-DOT-CENTER-DOT-CENTER-DOT-CLF BY ROTATIONAL SPECTROSCOPY [J].
BLOEMINK, HI ;
HINDS, K ;
LEGON, AC ;
HOLLOWAY, JH .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1995, (18) :1833-1834
[3]   CONFORMATIONS OF HYDROGEN-BONDED DIMERS FORMED BY CYCLIC ETHERS WITH HYDROGEN-FLUORIDE - ROTATIONAL SPECTRUM OF 2,5 DIHYDROFURAN=HF [J].
COLLINS, RA ;
MILLEN, DJ ;
LEGON, AC .
JOURNAL OF MOLECULAR STRUCTURE, 1987, 162 (1-2) :31-40
[4]   Stark-Zeeman hyperfine structure of (HBr)-Br-79 and (HBr)-Br-81 by molecular-beam electric-resonance spectroscopy [J].
Dabbousi, O. B. ;
Meerts, W. L. ;
De Leeuw, F. H. ;
Dymanus, A. .
CHEMICAL PHYSICS, 1973, 2 (04) :473-477
[5]   SUBMILLIMETER-WAVE SPECTRA AND EQUILIBRIUM STRUCTURES OF HYDROGEN HALIDES [J].
DELUCIA, FC ;
HELMINGER, P ;
GORDY, W .
PHYSICAL REVIEW A-GENERAL PHYSICS, 1971, 3 (06) :1849-+
[6]  
ENGERHOLM GG, 1965, THESIS U CALIFORNIA
[7]   INORGANIC STEREOCHEMISTRY [J].
GILLESPIE, RJ ;
NYHOLM, RS .
QUARTERLY REVIEWS, 1957, 11 (04) :339-380
[8]   DERIVATION OF RS STRUCTURE BY USE OF A NONDIAGONAL WEIGHT MATRIX FOR ROTATIONAL CONSTANTS [J].
HIROSE, C .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1974, 47 (04) :976-979
[9]  
Legon A.C., 1992, ATOMIC MOL BEAM METH, V2
[10]   CAN THE NONLINEARITY OF HYDROGEN-BONDS B...HX BE MEASURED PRECISELY - A METHOD FROM ROTATIONAL SPECTROSCOPY AND ITS APPLICATION TO 2,5-DIHYDROFURAN...HCL [J].
LEGON, AC ;
THORN, JC .
CHEMICAL PHYSICS LETTERS, 1994, 227 (4-5) :472-479