Trends in vibrational frequencies of guests trapped in clathrate hydrate cages

被引：171

作者：

Subramanian, S ^{[1
]}

Sloan, ED ^{[1
]}

机构：

[1] Colorado Sch Mines, Dept Chem Engn, Ctr Hydrate Res, Golden, CO 80401 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 2002年 / 106卷 / 17期

关键词：

D O I：

10.1021/jp013644h

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：

Raman spectra of ethane trapped in the small 5(12) cage of sII hydrate (at similar to70 MPa), isobutane trapped in the large 5(12)6(4) cage of sII hydrate, and the gauche form of n-butane trapped in the large 5(12)6(4) cage of sII hydrate were obtained for the first time. These new Raman results are combined with existing Raman and IR results for various guests to infer general trends in vibrational frequencies of guest molecules trapped in clathrate hydrate cages as a function of cage size, guest size, guest vibrational mode, and pressure. The observed trend in stretching frequencies of guests with cage size, which can be stated as "the larger the cavity, the lower the frequency", is explained through the qualitative "loose cage-tight cage" model of Pimentel and Charles.

引用

页码：4348 / 4355

页数：8

共 41 条

[1] INFRARED SPECTRA AND GEOMETRY OF SO2 ISOTOPES IN SOLID KRYPTON MATRICES [J].

ALLAVENA, M ;

RYSNIK, R ;

WHITE, D ;

CALDER, V ;

MANN, DE .

JOURNAL OF CHEMICAL PHYSICS, 1969, 50 (08) :3399-+

[2]

BARNES AJ, 1973, VIB SPECTROSC, pCH4

[3]

BATES FE, 1978, THESIS U ALBERTA

[4] SOLVENT EFFECTS IN INFRA-RED SPECTROSCOPY [J].

BUCKINGHAM, AD .

PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1958, 248 (1253) :169-182

[5] RAMAN-SPECTRA OF METHYL HALIDES AS GUEST MOLECULES IN BETA-QUINOL CLATHRATES - EVIDENCE FOR C-BR BOND COMPRESSION [J].

CLEAVER, KD ;

DAVIES, JED ;

WOOD, WJ .

JOURNAL OF MOLECULAR STRUCTURE, 1975, 25 (01) :222-224

[6] INFRARED-SPECTRA OF THE CLATHRATE HYDRATES OF ACETYLENE AND OF ACETYLENE ACETONE [J].

CONSANI, K ;

PIMENTEL, GC .

JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (02) :289-293

[7]

CULBERSON OL, 1951, T AM I MIN MET ENG, V192, P223

[8] MOTION OF GUEST MOLECULES IN CLATHRATE HYDRATES [J].

DAVIDSON, DW .

CANADIAN JOURNAL OF CHEMISTRY, 1971, 49 (08) :1224-&

[9] CHARACTERIZATION OF NATURAL-GAS HYDRATES BY NUCLEAR MAGNETIC-RESONANCE AND DIELECTRIC-RELAXATION [J].

DAVIDSON, SW ;

GARG, SK ;

GOUGH, SR ;

HAWKINS, RE ;

RIPMEESTER, JA .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1977, 55 (20) :3641-3650

[10] BARRIER TO ASYMMETRIC INTERNAL-ROTATION, CONFORMATIONAL STABILITY, VIBRATIONAL-SPECTRA AND ASSIGNMENTS, AND ABINITIO CALCULATIONS OF NORMAL-BUTANE-D0, NORMAL-BUTANE-D5 AND NORMAL-BUTANE-D10 [J].

DURIG, JR ;

WANG, A ;

BESHIR, W ;

LITTLE, TS .

JOURNAL OF RAMAN SPECTROSCOPY, 1991, 22 (11) :683-704

← 1 2 3 4 5 →