Spectroscopic probe of free volume changes at freezing: Raman scattering from CS2 in cyclohexane

D W N  Edington; P R L  Markwick; Wilson Poon; H  Vass; J  Crain

doi:10.1103/PhysRevLett.82.3827

Spectroscopic probe of free volume changes at freezing: Raman scattering from CS2 in cyclohexane

D W N Edington, P R L Markwick, Wilson Poon, H Vass, J Crain

School of Physics and Astronomy

Research output: Contribution to journal › Article › peer-review

Abstract / Description of output

We study the reorientational dynamics of CS2 molecules dissolved in cyclohexane, which undergoes a temperature-induced liquid to plastic crystal transition. Rotational correlation functions of the CS2 are obtained from Fourier inversion of polarized Raman scattering line shapes. Just below the plastic crystalline transition, the short-time reorientation rate increases with decreasing temperature. The same measurements on CS2 in n-propanol (which vitrifies at low temperatures) show a monotonic slowdown of short-time dynamics across the glass transition temperature. These results may provide the first direct evidence of the increase in local free volume accompanying the freezing of simple liquids.

Original language	English
Pages (from-to)	3827-3830
Number of pages	4
Journal	Physical Review Letters
Volume	82
Issue number	19
DOIs	https://doi.org/10.1103/PhysRevLett.82.3827
Publication status	Published - 10 May 1999

Keywords / Materials (for Non-textual outputs)

HIGH-PRESSURE RAMAN
ROTATIONAL RELAXATION
DYNAMICS
FLUID
REORIENTATION

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10.1103/PhysRevLett.82.3827

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title = "Spectroscopic probe of free volume changes at freezing: Raman scattering from CS2 in cyclohexane",

abstract = "We study the reorientational dynamics of CS2 molecules dissolved in cyclohexane, which undergoes a temperature-induced liquid to plastic crystal transition. Rotational correlation functions of the CS2 are obtained from Fourier inversion of polarized Raman scattering line shapes. Just below the plastic crystalline transition, the short-time reorientation rate increases with decreasing temperature. The same measurements on CS2 in n-propanol (which vitrifies at low temperatures) show a monotonic slowdown of short-time dynamics across the glass transition temperature. These results may provide the first direct evidence of the increase in local free volume accompanying the freezing of simple liquids.",

keywords = "HIGH-PRESSURE RAMAN, ROTATIONAL RELAXATION, DYNAMICS, FLUID, REORIENTATION",

author = "Edington, {D W N} and Markwick, {P R L} and Wilson Poon and H Vass and J Crain",

year = "1999",

month = may,

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doi = "10.1103/PhysRevLett.82.3827",

language = "English",

volume = "82",

pages = "3827--3830",

journal = "Physical Review Letters",

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T1 - Spectroscopic probe of free volume changes at freezing: Raman scattering from CS2 in cyclohexane

AU - Edington, D W N

AU - Markwick, P R L

AU - Poon, Wilson

AU - Vass, H

AU - Crain, J

PY - 1999/5/10

Y1 - 1999/5/10

N2 - We study the reorientational dynamics of CS2 molecules dissolved in cyclohexane, which undergoes a temperature-induced liquid to plastic crystal transition. Rotational correlation functions of the CS2 are obtained from Fourier inversion of polarized Raman scattering line shapes. Just below the plastic crystalline transition, the short-time reorientation rate increases with decreasing temperature. The same measurements on CS2 in n-propanol (which vitrifies at low temperatures) show a monotonic slowdown of short-time dynamics across the glass transition temperature. These results may provide the first direct evidence of the increase in local free volume accompanying the freezing of simple liquids.

AB - We study the reorientational dynamics of CS2 molecules dissolved in cyclohexane, which undergoes a temperature-induced liquid to plastic crystal transition. Rotational correlation functions of the CS2 are obtained from Fourier inversion of polarized Raman scattering line shapes. Just below the plastic crystalline transition, the short-time reorientation rate increases with decreasing temperature. The same measurements on CS2 in n-propanol (which vitrifies at low temperatures) show a monotonic slowdown of short-time dynamics across the glass transition temperature. These results may provide the first direct evidence of the increase in local free volume accompanying the freezing of simple liquids.

KW - HIGH-PRESSURE RAMAN

KW - ROTATIONAL RELAXATION

KW - DYNAMICS

KW - FLUID

KW - REORIENTATION

U2 - 10.1103/PhysRevLett.82.3827

DO - 10.1103/PhysRevLett.82.3827

M3 - Article

SN - 0031-9007

VL - 82

SP - 3827

EP - 3830

JO - Physical Review Letters

JF - Physical Review Letters

IS - 19

ER -

Spectroscopic probe of free volume changes at freezing: Raman scattering from CS2 in cyclohexane

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Keywords / Materials (for Non-textual outputs)

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