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

[21] POLYHEDRAL CLATHRATE HYDRATES .9. STRUCTURE OF ETHYLENE OXIDE HYDRATE [J].

MCMULLAN, RK ;

JEFFREY, GA .

JOURNAL OF CHEMICAL PHYSICS, 1965, 42 (08) :2725-&

[22] Structure and stability of ethane hydrate crystal [J].

Morita, K ;

Nakano, S ;

Ohgaki, K .

FLUID PHASE EQUILIBRIA, 2000, 169 (02) :167-175

[23] INFRARED SPECTRA OF CLCN IN MATRIX ISOLATION AND ANHARMONIC INTRAMOLECULAR FORCE FIELD [J].

MURCHISON, CB ;

OVEREND, J .

SPECTROCHIMICA ACTA PART A-MOLECULAR SPECTROSCOPY, 1971, A 27 (09) :1509-+

[24] HARMONIC FORCE-FIELD AND RAMAN-SCATTERING INTENSITY PARAMETERS OF NORMAL-BUTANE [J].

MURPHY, WF ;

FERNANDEZSANCHEZ, JM ;

RAGHAVACHARI, K .

JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (03) :1124-1139

[25] VIBRATIONAL-SPECTRA AND CONFORMATIONAL STABILITY OF NORMAL-BUTANE - COMMENT [J].

MURPHY, WF .

JOURNAL OF RAMAN SPECTROSCOPY, 1992, 23 (07) :413-415

[26] High-pressure phase equilibrium and Raman microprobe spectroscopic studies on the methane hydrate system [J].

Nakano, S ;

Moritoki, M ;

Ohgaki, K .

JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1999, 44 (02) :254-257

[27] High-pressure phase equilibrium and Raman microprobe spectroscopic studies on the CO2 hydrate system [J].

Nakano, S ;

Moritoki, M ;

Ohgaki, K .

JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1998, 43 (05) :807-810

[28] THE STRUCTURE OF MOLECULAR COMPOUNDS .3. CRYSTAL STRUCTURE OF ADDITION COMPLEXES OF QUINOL WITH CERTAIN VOLATILE COMPOUNDS [J].

PALIN, DE ;

POWELL, HM .

JOURNAL OF THE CHEMICAL SOCIETY, 1947, (FEB) :208-221

[29] Raman spectroscopic and statistical studies on natural clathrates from the Greenland Ice Core Project ice core, and neutron diffraction studies on synthetic nitrogen clathrates [J].

Pauer, F ;

Kipfstuhl, J ;

Kuhs, WF .

JOURNAL OF GEOPHYSICAL RESEARCH-OCEANS, 1997, 102 (C12) :26519-26526

[30]

Pimentel G. C., 1963, Pure Appl. Chem, V7, P111, DOI DOI 10.1351/PAC196307010111

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