Tetrahydrofuran, a water-soluble cyclic ether molecule, is well known for its ability to form clathrate hydrates (cubic structure II, melting point 277.5 K). An aqueous solution of THF (17:1 molecular ratio) was hyperquenched (cooled at a rate of 106Ks−1) to 77 K to give recoverable samples of ∼1 g of metastable amorphous material. The crystallization process was studied on three complementary length scales by x-ray powder diffraction, quadrupole echo double resonance (QEDOR) NMR spectroscopy, and Raman spectroscopy as the amorphous material was annealed at temperatures between 80 and 190 K. Results show that phase separation of the two components occurred predominantly during the annealing process, resulting in clusters of crystalline THF and ice Ic before clathrate hydrate crystallization was initiated. During the hyperquenching process, the decreasing molecular mobility of water molecules between room temperature and the fictive temperature (the temperature below which the solution becomes structurally immobilized upon hyperquenching) inhibits growth of the crystal nuclei that normally would result in crystalline clathrate hydrate formation. Annealing the samples between 110–140 K showed that the local hydrogen bonded O–H--O structure of the water molecules changed toward the arrangement characteristic of crystalline ice Ic. We propose that this process forces the THF out of the glassy solution, thus increasing the THF cluster size in the deposit so that these become visible to diffraction. Further annealing, above 150–160 K caused large-scale growth of crystalline clathrate hydrate material, which then could be associated with a reduction in the THF cluster size, and ice Ic.

1.
O.
Mishima
,
L. D.
Calvert
, and
E.
Whalley
,
Nature (London)
310
,
393
(
1984
).
2.
P.
Handa
,
O.
Mishima
, and
E.
Whalley
,
J. Chem. Phys.
84
,
2766
(
1986
).
3.
E.
Mayer
,
J. Appl. Phys.
58
,
663
(
1985
).
4.
A. H.
Narten
,
C. G.
Venkatesh
, and
S. A.
Rice
,
J. Chem. Phys.
64
,
1106
(
1976
).
5.
A.
Bizid
,
L.
Bosio
,
A.
Defrain
, and
M.
Oumezzine
,
J. Chem. Phys.
87
,
2225
(
1987
).
6.
M. C.
Bellissent-Funel
,
L.
Bosio
,
A.
Hallbruker
,
M.
Mayer
, and
R.
Sridi–Dorbez
,
J. Chem. Phys.
97
,
1
(
1992
).
7.
M. G. Sceats and S. A. Rice, in Water a Comprehensive Treatise, edited by F. Franks, (Plenum, New York, 1982), Vol. 7, p. 83.
8.
D. D.
Klug
,
O.
Mishima
, and
E.
Whalley
,
J. Chem. Phys.
86
,
5323
(
1987
).
9.
E.
Mayer
,
J. Phys. Chem.
89
,
3474
(
1985
).
10.
J. A.
Ripmeester
,
C. I.
Ratcliffe
, and
D. D.
Klug
,
J. Chem. Phys.
96
,
8503
(
1992
).
11.
G. P.
Johari
,
A.
Hallbrucker
, and
E.
Mayer
,
Science
273
,
90
(
1996
).
12.
J. A.
McMillan
and
S. C.
Los
,
Nature (London)
206
,
806
(
1965
).
13.
G. P.
Johari
,
A.
Hallbruker
, and
E.
Mayer
,
Nature (London)
330
,
552
(
1987
).
14.
R. J.
Speedy
,
J. Phys. Chem.
96
,
2322
(
1992
).
15.
G. P.
Johari
,
G.
Flaissner
,
A.
Hallbruker
, and
E.
Mayer
,
J. Phys. Chem.
98
,
4719
(
1994
).
16.
R. J.
Speedy
,
P. G.
Dedenedetti
,
R. S.
Smith
,
C.
Huang
, and
B. D.
Kay
,
J. Chem. Phys.
105
,
240
(
1996
).
17.
M.
Fisher
and
J. P.
Devlin
,
J. Phys. Chem.
99
,
11584
(
1995
).
18.
G.
Fleissner
,
A.
Hallbrucker
, and
E.
Mayer
,
J. Phys. Chem.
99
,
8401
(
1995
).
19.
R. S.
Smith
,
C.
Huang
, and
B. D.
Kay
,
J. Phys. Chem. B
101
,
6123
(
1997
).
20.
G. A. Jeffrey, in Comprehensive Supramolecular Chemistry, edited by J. L. Atwood, J. E. D. Davis, D. D. MacNicol, and F. Vögtle (Pergamon, New York, 1996), Vol. 6, p. 757.
21.
Annals of the New York Academy of Sciences, edited by E. D. Sloan, J. Happel, and M. A. Hnatow (The New York Academy of Sciences, New York, 1994), vol. 715.
22.
T.
Head-Gordon
,
Proc. Natl. Acad. Sci. USA
92
,
8308
(
1995
).
23.
J.
Long
and
E. D.
Sloan
, Jr.
,
Mol. Simul.
11
,
145
(
1993
).
24.
J.
Hernandez
,
N.
Uras
, and
J. P.
Devlin
,
J. Phys. Chem. B
102
,
4526
(
1998
).
25.
F.
Fleyfel
and
J. P.
Devlin
,
J. Phys. Chem.
95
,
3811
(
1991
).
26.
A.
Hallbrucker
,
J. Chem. Soc., Faraday Trans.
90
,
293
(
1994
).
27.
A.
Hallbruker
and
E.
Mayer
,
J. Phys. Chem.
91
,
503
(
1987
).
28.
P.
Luger
and
J.
Buschmann
,
J. Angew. Int. Ed. Engl.
22
,
410
(
1983
).
29.
D. W. Davidson, in Water A Comprehensive Treatise, edited by F. Franks, (Plenum, New York, 1973), Vol. 2, p. 115.
30.
B.
Kamb
,
Trans. Am. Crystallogr. Assoc.
5
,
61
(
1969
).
31.
Y.
Ba
,
C. I.
Ratcliffe
, and
J. A.
Ripmeester
,
Chem. Phys. Lett.
299
,
201
(
1999
).
32.
S. K.
Garg
,
D. W.
Davidson
, and
J. A.
Ripmeester
,
J. Magn. Reson.
15
,
295
(
1974
).
33.
The Raman data indicate that some THF deposits from the vapor phase and crystallizes on the surface of the hyperquenched droplets. This contributes no more than 5% to the total NMR response.
34.
M. G. Sceats and S. A. Rice, in Water A Comprehensive Treatise, edited by F. Franks, (Plenum, New York, 1982), Vol. 7, p. 83.
35.
The interpretation of such spectra is difficult and for many years a detailed understanding of the origin of these modes was limited. An intuitive understanding comes from Whalley’s comparison of similar spectra obtained from ordered high pressure ice VIII and disordered ice VII, and then comparing these with spectra from ordered and disordered ice Ic. It was also noted that the spectra of ice Ic and ice Ih were virtually indistinguishable. The Raman active mode giving the most intense spectral band is centered at 3083 cm−1 and was assigned mainly to coupled ν1 vibrations moving in phase. Strong evidence for these ideas came from Haas and Hornig who used infrared spectroscopy to study the isolated O–D and O–H vibrations as a function of HDO concentration in H2O and D2O. Recently, the molecular vibrations of D2O ice were calculated by ab initio MD simulations with the NCC potential.
36.
E.
Whalley
,
Can. J. Chem.
55
,
3429
(
1977
).
37.
C.
Haas
and
D. F.
Hornig
,
J. Chem. Phys.
32
,
1763
(
1960
).
38.
F.
Sciortino
and
G.
Corongiu
,
J. Chem. Phys.
98
,
5694
(
1993
).
39.
D. D.
Klug
,
O.
Mishima
, and
E.
Whalley
,
J. Chem. Phys.
86
,
5323
(
1987
).
40.
B.
Cadioli
,
E.
Gallinella
,
C.
Coulombeau
,
H.
Jobic
, and
G.
Berthier
,
J. Chem. Phys.
97
,
7844
(
1993
).
41.
C. A.
Tulk
,
D. D.
Klug
,
R.
Branderhorst
,
P.
Sharpe
, and
J. A.
Ripmeester
,
J. Chem. Phys.
109
,
8478
(
1998
).
42.
E. Whalley, in The Hydrogen Bond, edited by P. Schuster, G. Zundel, and C. Sandorfy (North-Holland, Amsterdam, 1976), Vol. III, p. 1425.
43.
G. S. Kell, in Water: A Comprehensive Treatise, edited by F. Franks, (Plenum, New York, 1972), Vol. 1, p. 363.
44.
G.
Fleissner
,
A.
Hallbrucker
, and
E.
Mayer
,
J. Phys. Chem.
102
,
6239
(
1998
).
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