Structure and thermal expansivity of tetrahydrofuran deuterate determined by neutron powder diffraction

被引:39
作者
Jones, CY
Marshall, SL
Chakoumakos, BC
Rawn, CJ
Ishii, Y
机构
[1] Oak Ridge Natl Lab, Oak Ridge, TN 37831 USA
[2] Japan Atom Energy Res Inst, Naka, Ibaraki 3111195, Japan
关键词
D O I
10.1021/jp020513n
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
The crystal structure of tetrahydrofuran deuterate, a clathrate hydrate, has been refined from neutron powder diffraction data at five temperatures in the range 7-265 K. The thermal expansivity was shown to be greater than that of ice Ih in the same range of temperature (7), as observed in previous studies of other clathrates. The overall effect of T has been resolved into contributions from different geometrical parameters in the structure. Thus, an increase in T results in expansion of the host-lattice framework with increases in both the D-D and O-O distances and out-of-plane tilting of water molecules. The greatest dependence on T is exhibited by the D-D distances and the distortion of the hexagonal faces from planarity, which is particularly pronounced in the range 75-140 K. The cage volumes show a complex dependence on T. from 7 to 140 K, the volume of the small cage decreases slightly and that of the large cage increases, and between 140 and 205 K, the trend is reversed. The most pronounced structural changes occur in a similar regime of T as changes in guest dynamics observed in spectroscopic and thermodynamic studies. The temperature dependences of the structure and alpha(T), when considered along with the relation of (x(T) to the degree of anharmonicity in bonding,(34) could be formulated to provide a sensitive test of molecular models of clathrate hydrates.
引用
收藏
页码:6026 / 6031
页数:6
相关论文
共 37 条
[1]   Dynamic properties of the tetrahydrofuran clathrate hydrate, investigated by solid state 2H NMR spectroscopy [J].
Bach-Vergés, M ;
Kitchin, SJ ;
Harris, KDM ;
Zugic, M ;
Koh, CA .
JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (14) :2699-2706
[2]   INFRARED-SPECTRA FROM 300 TO 10 CM-1 OF STRUCTURE-II CLATHRATE HYDRATES AT 4.3-DEGREES-K [J].
BERTIE, JE ;
JACOBS, SM .
JOURNAL OF CHEMICAL PHYSICS, 1978, 69 (09) :4105-4113
[3]  
BUELER B, 2000, POLYTOPES COMBINATOR, V29
[4]   A REINVESTIGATION OF THE STRUCTURE OF TETRAHYDROFURAN BY HIGH-RESOLUTION NEUTRON POWDER DIFFRACTION [J].
DAVID, WIF ;
IBBERSON, RM .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1992, 48 :301-303
[5]   DIELECTRIC ABSORPTION + MOLECULAR MOTION IN GAS HYDRATES [J].
DAVIDSON, DW ;
DAVIES, MM ;
WILLIAMS, K .
JOURNAL OF CHEMICAL PHYSICS, 1964, 40 (11) :3449-&
[6]   CRYSTALLOGRAPHIC STUDIES OF CLATHRATE HYDRATES .1. [J].
DAVIDSON, DW ;
HANDA, YP ;
RATCLIFFE, CI ;
RIPMEESTER, JA ;
TSE, JS ;
DAHN, JR ;
LEE, F ;
CALVERT, LD .
MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 1986, 141 (1-2) :141-149
[7]   MOTION OF GUEST MOLECULES IN CLATHRATE HYDRATES [J].
DAVIDSON, DW .
CANADIAN JOURNAL OF CHEMISTRY, 1971, 49 (08) :1224-&
[8]   NMR BEHAVIOR OF CLATHRATE HYDRATE OF TETRAHYDROFURAN .I. PROTON MEASUREMENTS [J].
GARG, SK ;
DAVIDSON, DW ;
RIPMEEST.JA .
JOURNAL OF MAGNETIC RESONANCE, 1974, 15 (02) :295-309
[9]   COMPOSITION OF TETRAHYDROFURAN HYDRATE AND EFFECT OF PRESSURE ON DECOMPOSITION [J].
GOUGH, SR ;
DAVIDSON, DW .
CANADIAN JOURNAL OF CHEMISTRY, 1971, 49 (16) :2691-&
[10]   DIELECTRIC PROPERTIES OF SOME CLATHRATE HYDRATES OF STRUCTURE II [J].
GOUGH, SR ;
HAWKINS, RE ;
MORRIS, B ;
DAVIDSON, DW .
JOURNAL OF PHYSICAL CHEMISTRY, 1973, 77 (25) :2969-2976