Chapter 4. Spectroscopic studies of intermolecular forces in dense phases

Yarwood, J.

doi:10.1039/pc9797600099

Cited by 26 publications

(15 citation statements)

References 2 publications

(2 reference statements)

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“…We have little to say about this problem other than to note that in almost all models employed for the t-dependence of correlation functions such as N (U~2(t)U~2(O)), one requires a knowledge of the zero-time ensemble average N(uD2(o)uD2(o)). For example, a commonly adopted approach [2][3][4][5][6] is to assume…”

Section: + N(c~ + C~)(udz(t~)ud2(o)} C + N2c~mentioning

confidence: 99%

“…The problem of vibrational relaxation in molecular liquids has attracted considerable attention in the last 10-15 years, and many notable advances in both theory and experiment have been achieved; for recent reviews see [1][2][3]. It is by now well established that three principal mechanisms contribute to vibrational relaxation in liquids, namely: environmental frequency fluctuations, resonant transfer of vibrational excitation (or resonant excitonic transfer), and vibrational population relaxation.…”

Section: Introductionmentioning

confidence: 99%

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On the isotropic Raman spectra of isotopic binary mixtures

Logan¹

1986

Molecular Physics

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A theory is developed for the isotropic Raman spectrum of nondegenerate modes in polyatomic binary mixtures. Particular emphasis is attached to isotopic binary mixtures and the problem of dipolar resonant transfer. The thermodynamic state dependences of spectral features are investigated in some detail. Attention is focused on quantities which are experimentally accessible by isotopic dilution experiments, in particular the frequency shift of the spectrum consequent upon isotopic dilution, and also the resultant changes in spectral second moments. The theory is compared with some existing experiments on specific systems, and a number of predictions are made which are capable of being tested experimentally.

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Section: + N(c~ + C~)(udz(t~)ud2(o)} C + N2c~mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

On the isotropic Raman spectra of isotopic binary mixtures

Logan¹

1986

Molecular Physics

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“…[1][2][3] Line shape analysis of vibrational transitions has long been recognized as a powerful tool for extracting information on molecular dynamics in condensed phases. 4,5 The difficulty with determining the microscopic dynamics from a spectrum arises because linear spectroscopic techniques have no method for separating the various contributions to the vibrational line shape. The IR absorption or Raman line shape represents a convolution of the various dynamic and static contributions to the observed line shape.…”

Section: Introductionmentioning

confidence: 99%

Homogeneous vibrational dynamics and inhomogeneous broadening in glass-forming liquids: Infrared photon echo experiments from room temperature to 10 K

Tokmakoff

Fayer

1995

The Journal of Chemical Physics

174

190

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A study of the temperature dependence of the homogeneous linewidth and inhomogeneous broadening of a high-frequency vibrational transition of a polyatomic molecule in three molecular glass-forming liquids is presented. Picosecond infrared photon echo and pump-probe experiments were used to examine the dynamics that give rise to the vibrational line shape. The homogeneous vibrational linewidth of the asymmetric CO stretch of tungsten hexacarbonyl ͑ϳ1980 cm Ϫ1 ͒ was measured in 2-methylpentane, 2-methyltetrahydrofuran, and dibutylphthalate from 300 K, through the supercooled liquids and glass transitions, to 10 K. The temperature dependences of the homogeneous linewidths in the three glasses are all well described by a T 2 power law. The absorption linewidths for all glasses are seen to be massively inhomogeneously broadened at low temperature. In the room temperature liquids, while the vibrational line in 2-methylpentane is homogeneously broadened, the line in dibutylphthalate is still extensively inhomogeneously broadened. The contributions of vibrational pure dephasing, orientational diffusion, and population lifetime to the homogeneous line shape are examined in detail in the 2-methylpentane solvent. The complete temperature dependence of each of the contributions is determined. For this system, the vibrational line varies from inhomogeneously broadened in the glass and low temperature liquid to homogeneously broadened in the room temperature liquid. The homogeneous linewidth is dominated by the vibrational lifetime at low temperatures and by pure dephasing in the liquid. The orientational relaxation contribution to the line is significant at some temperatures but never dominant. Restricted orientational relaxation at temperatures below ϳ120 K causes the homogeneous line shape to deviate from Lorentzian, while at higher temperatures the line shape is Lorentzian.

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“…In addition to the recent work using THz-TDS, over decades a large number of studies have been done using low-frequency Raman spectroscopy and far-IR spectroscopy to investigate similar effects, and we strongly recommend this literature and the references therein to the interested reader for more detailed information. [41][42][43][44][45][46][47][48] Supercooled Liquids and Glasses. Liquids.…”

Section: Mesoscopic Structure and Dynamicsmentioning

confidence: 99%

Terahertz Time-Domain and Low-Frequency Raman Spectroscopy of Organic Materials

2015

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With the ongoing proliferation of terahertz time-domain instrumentation from semiconductor physics into applied spectroscopy over the past decade, measurements at terahertz frequencies (1 THz [ 10 12 Hz [ 33 cm À1) have attracted a sustained growing interest, in particular the investigation of hydrogen-bonding interactions in organic materials. More recently, the availability of Raman spectrometers that are readily able to measure in the equivalent spectral region very close to the elastic scattering background has also grown significantly. This development has led to renewed efforts in performing spectroscopy at the interface between dielectric relaxation phenomena and vibrational spectroscopy. In this review, we briefly outline the underlying technology, the physical phenomena governing the light-matter interaction at terahertz frequencies, recent examples of spectroscopic studies, and the current state of the art in assigning spectral features to vibrational modes based on computational techniques.

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Chapter 4. Spectroscopic studies of intermolecular forces in dense phases

Cited by 26 publications

References 2 publications

On the isotropic Raman spectra of isotopic binary mixtures

On the isotropic Raman spectra of isotopic binary mixtures

Homogeneous vibrational dynamics and inhomogeneous broadening in glass-forming liquids: Infrared photon echo experiments from room temperature to 10 K

Terahertz Time-Domain and Low-Frequency Raman Spectroscopy of Organic Materials

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