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Dynamics of glass-forming liquids. IX. Structural versus dielectric relaxation in monohydroxy alcohols
Li-Min Wang and Ranko Richert
Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604

Received 9 August 2004; accepted 7 September 2004 The prominent Debye-type but non-Arrhenius dielectric relaxation is a feature common to many monohydroxy alcohols in their liquid state. Although this exponential process is often considered to reect the primary structural relaxation, only a faster, smaller, and nonexponential relaxation peak correlates with viscous ow and mechanical relaxation. We provide dielectric relaxation data for 2-methyl-1-butanol, 2-ethyl-1-hexanol, and 3,7-dimethyl-1-octanol across ten decades in time. Based on these and previous results, we show that there exists a variety of dielectric to mechanical relaxation time ratios in the viscous regime, but a universal value of 100 for that ratio appears to evolve in the high temperature limit. The temperature dependence for both the relaxation time and strength of the Debye peak differs from the typical behavior of structural dynamics in terms of the process. The implications of these ndings for rationalizing the Debye-type dielectric process of hydrogen-bonded liquids are discussed. 2004 American Institute of Physics. DOI: 10.1063/1.1811072

A common experimental approach to the dynamics of liquids is by dielectric relaxation techniques, where frequency dependent polarization in terms of the dielectric function * ( ) indicates the motion of charge in the sample as a response to an external electric eld.1 In molecular liquids that are free of charge carriers, the dielectric displacement originates from the orientational degrees of freedom of dipoles that are present in practically all molecules. Therefore, dielectric relaxation measurements yield very direct information about the molecular motion, although strictly speaking the macroscopic dipole moment is the relevant quantity.2 Molecular orientation can be seen across particularly wide ranges of frequencies or times in the case of glassforming materials,3 where cooling the liquid gradually increases the time scale of viscous ow instead of an abrupt solidication by a liquid to crystal phase transition. These glass-forming liquids solidify at the glass transition temperature T g through a kinetic transition, at which the structural relaxation time exceeds some typical experimental time window, e.g., 100 s.4,5 Particularly important liquids are those where hydrogen bonding is a signicant aspect of the intermolecular interactions.6 Examples are water,7 primary alcohols,8 polyols,9 sugars,10 and their aqueous solutions.11 Typical glass-forming candidates with hydrogen-bonding capabilities are 1-propanol,12,13 ethanol,14 glycerol,15,16 propylene glycol,17,18 D-sorbitol,19,20 salol,21,22 and a number of alcohols with branched alkyl structure. Naturally, such liquids exhibit high polarities and their dielectric relaxations are easily observed in experimental studies. Contrary to simple van der Waals liquids, a number of hydrogen-bonding systems display a pronounced dielectric Debye process together with other loss components at higher frequencies, often exhibiting three distinct dielectric modes. The microscopic mechanisms behind this unusual dielectric behavior of associating liquids has remained puzzling to date. Although associating mix0021-9606/2004/121(22)/11170/7/$22.00

tures can show such behavior as well, we will focus on single component liquids in what follows. The observation of a Debye-type or only slightly broadened dielectric loss prole in a molecular liquid is not unusual in the domain of dynamics exceeding frequencies around 10 GHz, but the situation is different in supercooled liquids. Typical viscous liquids display non-Arrhenius and nonexponential dynamics with the extent of the two features being correlated quantities.23 However, some glass-forming hydrogen-bonding liquids, e.g., 1-propanol, depart signicantly from Arrhenius behavior, while the prominent dielectric relaxation feature is characterized by a single time constant, equivalent to a purely exponential or Debye-type process.24 A closer scrutiny reveals the existence of three distinct contributions to the total dielectric relaxation spectrum and much work has been devoted to understanding the microscopic origin of these processes.2527 More denitive assignments of these dielectric modes to the respective molecular motions are important also for the elds of chemical kinetic and solvation processes, to which the dielectric properties serve as crucial input.28 30 The combination of a prominent Debye peak with additional higher frequency losses are being observed across the entire liquid and supercooled regime of a number of hydrogen-bonding materials. Opposed to very uid systems, the dynamics in the supercooled state bear the advantage that molecular motions associated with viscous ow usually exhibit nonexponential loss peaks which are then easily discriminated from the prominent Debye feature of present interest. The aim of the present work is to provide additional insight into the Debye relaxation in glass-forming monohydroxy alcohols with emphasis on the spectral separation between the Debye peak ( D) and the structural relaxation ( ) . For cases where the Debye process is more than a 1000 slower than the time scales associated factor of D / with viscous ow, it is obvious that unlike simple molecular liquids the prominent lowest frequency dielectric relaxation
2004 American Institute of Physics


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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004

Dynamics of glass-forming liquids. IX


is not the signature of structural relaxation. Although the time scale ratio D / varies between 14 and 2000 for different alcohols near T g , we demonstrate that this spectral offset approaches a common value of D / 100 in the high temperature limit. Additionally, the decrease of the Debye relaxation strength D with increasing temperature differs from the pattern observed for the primary or -relaxation peaks.

The linear primary alcohols Cn H2n 1 OH tend to crystallize at common cooling rates except for 1-propanol. Analogous to the glass-forming ability of linear versus branched alkanes, branched compounds with -OH end groups are good glass formers. The present dielectric measurements were performed on 2-methyl-1-butanol 2M1B, 99 %), 2-ethyl-1hexanol 2E1H, 99 %) and 3,7-dimethyl-1-octanol DM1O, 99% . All chemicals are purchased form Aldrich and used as received. The dielectric measurements are conducted by holding the liquid between two brass electrodes which are separated by thin Teon strips arranged in a radial geometry. The dimensions of this capacitor with 20 mm diameter and 50 or 25 m thickness result in the respective geometric capacities of C 0 55.6 or 111.2 pF. All samples are measured inside a nitrogen-gas cryostat where the temperature is stabilized and measured by a Novocontrol Quatro controller. The stability of the temperature reading is better than 0.05 K. Frequency dependent impedance measurements were performed using a Solartron 1260 gain-phase analyzer equipped with a Mestec DM-1360 transimpedance amplier. Data are acquired for frequencies in the range 1010 MHz, with the frequencies being logarithmically spaced at a density of 8 per decade. This impedance technique requires a reference measurement in order to calibrate the frequency dependent transimpedance Z( ) of the DM-1360.31 For the present case, the empty sample capacitor turned out to be appropriate. For the monohydroxy alcohols, the frequency dependent dielectric curves include four distinct features: the dc conrelaxductivity, a Debye-type D relaxation, a primary ation peak, and a secondary relaxation peak. In order to quantify the characteristics of these processes as a function of temperature, we follow common practice and subject the dielectric relaxation data to the following empirical t function which combines the Havriliak-Negami32 type with several of its special cases,

FIG. 1. Real part ( ) of the dielectric spectrum of 2-methyl-1-butanol vs frequency. In the order of increasing transition frequency, the curves are for temperatures from 130 to 180 K in steps of 2 K and from 184 to 220 K in steps of 4 K. The ordinate is scaled logarithmically in order to show the two individual contributions in the ranges 2.0 2.8 and 2.8 31.

tion used to reect the asymmetrically broadened proles of the primary process, with and characterizing the symmetric and asymmetric broadening, respectively. The secondary relaxation addressed in the fourth term is usually well described by the symmetric Cole-Cole function, equivalent 1. In this paper, we will not to the HN expression with discuss the slow secondary or relaxation, though we found clear peaks in some of the alcohols. Finally, the dc conductivity gauged by dc is included in order to obtain reliable t parameters for the dielectric peaks, but remains disregarded otherwise.


dc 0i

i , 1

is the dielectric constant in the high-frequency where limit. The parameters D and D are the relaxation strength and time of the prominent process of lowest peak frequency, and refer to the primary structural or prowhile cess. The second term of this equation represents a Debye function and the third term a Havriliak-Negami HN func-

As expected, the dielectric measurements of the present alcohols show dominant slow Debye-type dielectric relaxation peaks with high dielectric strength D and subsequent non-Debye contributions of signicantly lower amplitudes positioned at higher frequencies. The results of 2-methyl-1butanol are shown as permittivity spectra ( ) for various temperatures in Fig. 1, using a logarithmic ordinate scale in order to visualize the distinct processes. The case of T 142 K is displayed in Fig. 2 in a Cole-Cole diagram, where a semicircle with a center positioned on the abscissa indicates a Debye process. The main panel of Fig. 2 enlarges the additional higher frequency and lower amplitude features. The behavior of Figs. 1 and 2 is typical for the three liquids of this study: A superposition of a large Debye-type signal and additional dispersive relaxation processes which are offset several decades towards higher frequencies ( D ) and signicantly smaller regarding their relaxation strength ). ( D An activation plot of the relaxation times of both the relaxation as a Debye process D and the non-Debye function of reciprocal temperature is presented in Fig. 3. Each curve exhibits the non-Arrhenius feature with obvious

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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004

L.-M. Wang and R. Richert

FIG. 2. Cole-Cole representation, ( ) vs ( ), of the higher frequency component of the dielectric response of 2-methyl-1-butanol at T 142 K. The symbols are the experimental results in the frequency range 6 Hz2 MHz. The inset displays the complete curve for the frequency range 40 mHz2 MHz. In each panel, the solid line represents a t to the Debye peak and relaxation with 1.96, 0.87, D 29.7, D 0.23 s, 0.77 ms, 0.57, and 0.52. The dashed line shows the Debye component of the t.

spectral separation of the two distinct dynamics, and they can be tted well with the Vogel-Fulcher-Tammann VFT equation,33 log10 /s A B/ T T 0 , 2

implying a kinetic arrest if extrapolated to a nite temperature T T 0 . However, visual inspection of Fig. 3 and more quantitatively VFT ts to D(T) and (T) show that the spectral separation between Debye and peak is material specic and temperature dependent. At a common peak frequency of D 0.3 Hz for the Debye peak, the time scale ratios D / for the three liquids in Fig. 3 span a range of 14 2000 numbers in parentheses of Fig. 3 . Towards higher temperatures and faster dynamics, the ratios D / appear to become more uniform. In order to inspect this trend further, Fig. 4 compiles graphically how the peak frequency of the process ( ) varies with that of the Debye frequency ( D) . This graph also includes previously obtained data on the glass-forming alcohols 1-propanol, ethanol, and 5-methyl-2hexanol and high frequency results for methanol and dodecanol. In the case of ethanol, the analysis of Brand et al. resulted in a non-Debye curve for the lowest frequency dielectric peak for T 130 K. 14 A comparison with the behavior of other monohydroxy alcohols suggests, however, that a Debye and nearby -peak plus a slow secondary relaxation will t the observed dielectric data of ethanol as well. The inset of Fig. 4 emphasizes that some curves do not depart substantially from log10( / D) 2, while the present results for 2M1B, 2E1H, and DM1O are subject to larger variations in the viscous regime. The results of Fig. 4 support the notion that a common spectral separation of peak frequencies / D or of relaxation times D / by a factor of 100 is achieved in the limit of high temperatures, irrespective of the material specic lower temperature value. This observation of D not exceeding 1010 1011 Hz implies that, unlike struc-

FIG. 3. Activation maps of the relaxation times, log10( /s) vs 1/T, of the Debye ( D , open symbols and main non-Debye ( , solid symbols dielectric relaxation modes for three glass-forming alcohols in their viscous regimes, 2-methyl-1-butanol 2M1B , 2-ethyl-1-hexanol 2E1H , and 3,7dimethyl-1-octanol DM1O . The numbers in parentheses designate the time scale ratio D / determined at a common peak frequency of D 0.3 Hz for the Debye peak.

tural dynamics, the Debye peak will not reach phonon frequencies around 1013 Hz in the limit of T .

To set the stage for what follows, we will need to specify in more detail the dielectric signatures of the liquids of current interest. Relatively narrow dielectric relaxation patterns can be found at sufciently high temperatures or in systems characterized by a strong, i.e., Arrhenius-like, temperature dependence of the relaxation time.4 The case of present concern is the situation of a true Debye process seen as the lowest frequency feature combined with additional higher frequency modes of much smaller amplitudes.8,13,24 If this situation is encountered in a glass-forming material, the complex loss pattern remains upon cooling to the glass transition temperature T g . For the well investigated case of 1-propanol, three distinct relaxation modes are found at microwave frequencies as well as in the slow response of the viscous regime near T g . 30 However, it is important to realize that these three dielectric modes observed at high and low frequencies are of different origin: At frequencies below 10 MHz, three distinct peaks are seen in 1-propanol, the prominent Debye peak, a smaller asymmetrically broadened peak at higher frequencies, and an even smaller but symmetric peak at even higher frequencies. It has been argued that

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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004

Dynamics of glass-forming liquids. IX


FIG. 4. Temperature dependent peak frequencies for various alcohols shown as peak frequency of the second non-Debye peak ( ) versus that of the prominent Debye peak ( D) . The variation of the logarithmic ratio, log10( / D) near T g between 1.1 and 3.3 gradually reduces to a common value of 2 in the limit of high temperatures. Data for 1-propanol are taken from Ref. 24, those for ethanol are from Ref. 14, and 5-methyl-2-hexanol data are from Ref. 39. The single high frequency point for methanol is from Ref. 67, that for dodecanol is from Ref. 44.

the two faster components display all the characteristic properties of an and relaxation of a typical nonassociating glass former.24,34 The and processes merge at a temperature T , at which the peak frequencies are near 10 MHz, and only a single structural relaxation peak remains at higher temperatures. At room temperature, Garg and Smith have analyzed the high frequency dielectric absorption that appears in excess of the prominent Debye peak.35 Because of the limited number of available frequencies and because of the common practice to analyze in terms of Debye processes, two such peaks were invoked in order to t the entire loss because the actual shape of the peak is broader than a single Debye curve. Therefore, the two faster Debye peaks reported for room temperature should be understood as an approximation to the actually asymmetrically broadened relaxation. For the typical case of 2-methyl-1-butanol, Fig. 2 demonstrates that the high frequency contributions are well described by a HN function instead of indicating multimodal structure. In summary, these dielectric spectra are well characterized by two peaks, a Debye and a smaller HN-type peak, across the entire dynamic range, plus a symmetric secondary peak that occurs only below a frequency of 10 MHz. Another important observation refers to the fact that not all alcohols or other liquids capable of hydrogen bonding will display the dielectric scenario of current interest. Regarding hydroxyl compounds, the Debye feature is limited to certain monohydroxy alcohols,36 39 and remains absent in diols propylene glycol, pentanediols ,17,40 and polyols glycerol, sorbitol, sugars .9,15,20 In other cases, sterical hindrance of the hydrogen bond is made responsible for the lack of a Debye peak.41,42 In alkane/alcohol mixtures, the largest dielectric peak remains Debye-like up to signicant but not too high alkane fractions.43,44 For amides with weaker hydrogen bonds compared with alcohols, it is interesting that

N-substituted amides such as N-methylformamide display a Debye peak, while formamide and N,N-dimethylformamide do not.45 Given that the above phenomenology is limited to hydrogen-bonding systems, it is natural to associate the Debye-type dielectric feature with specic properties of the hydrogen-bonding character of the -OH group in these liquids. It has been recognized early on that the dielectric strengths seen in many alcohols are not consistent with the independent rotational motion of alcohol molecules with dipole moments around 1.7 D. Excess permittivity of these strong Debye signals has been rationalized on the basis of Kirkwoods model of dipole correlations.46 It predicts higher lower effective dipole moments eff in the presence of nonelectrostatic orientational correlations which favor parallel antiparallel alignments. The effects are usually quantied 2 2 in terms of a correlation factor g is the eff/ , where true gas phase dipole moment of the molecules. For the alcohols of present interest, reported g values are above unity and approach unity only at sufciently high temperatures.25 The initial simple interpretation of Oster and Kirkwood required revision when Cole and co-workers realized the existence of a further secondary dielectric dispersion in addition to the Debye process.47 49 It was concluded that the Debye and secondary motion, respectively, originate from the orientation of OH and OR bonds, where R is the alkyl group. This interpretation implied that the reorientation of an OH bond requires the breaking of an intermolecular hydrogen bond and eventually the formation of a different bond. If breaking the H-bond is the rate determining step, the activation barrier will be a rather well dened quantity and should lead to an Arrhenius-type temperature dependence. In a study which compared mechanical with dielectric relaxation times, Litovitz and McDufe have observed that the ratio of time scales is 10 or less for many nonassociating liquids, while values exceeding 100 are encountered in the case of alcohols.50 Similarly, the glass-transition temperatures inferred from differential scanning calorimetry DSC on some alcohols fail to match the T g derived from the kinetic criterion g (T T g ) 100 s, while good agreement is found for simple glass-forming liquids,51,52 and for the small dielectric process of monohydroxy alcohols.36,37 More specically, a detailed DSC study of 1-propanol resulted in T g 96.2 K, 53 while the kinetic T g s are 101.9 K for the Debye peak and 97.0 K for the smaller process.24 Not only is the kinetic T g based upon the dielectric Debye feature at variance with the calorimetric result, but the kinetic criterion applied to the peak yields a value which is consistent with the T g derived from DSC. That the dielectrically small relaxation is the signature of structural relaxation is also supported by simultaneous dielectric and photon-correlation spectroscopy on viscous 1-propanol, indicating that the time scale of density-density correlations coincide with the process rather than with the Debye peak, which is a factor of 160 slower in 1-propanol.24 In the same study, viscosity data is seen to overlap with the -relaxation time, after the otherwise arbitrary - shift factor is determined by mechanical relaxation time results.24 Additionally, assigning the second largest and asymmetrically broadened dielectric process to

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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004

L.-M. Wang and R. Richert

FIG. 5. Activation map of the relaxation times, log10( /s) vs 1/T, of the Debye ( D , open circles and main non-Debye ( , solid circles dielectric relaxation modes for the glass-forming alcohol 2-methyl-1-butanol. The dashed line represents a VFT t to the solid circles with the parameters A 14, B 662 K, and T 0 78.6 K. Triangles are viscosity data taken from Refs. 59 and 60, log10( /Pa s) vs 1/T, scaled to the typical values of 2.5 1011 Pa s at T T g and 2.5 10 6 Pa s in the limit T (1 P 0.1 Pa s).

the structural relaxation restores the correlation between the KohlrauschWilliamsWatts54,55 or stretching exponent and the fragility index m seen for a large number of glass formers.56 Finally, dipolar and mechanical triplet solvation techniques, respectively, pick up the Debye and the peak only, emphasizing that the prominent dielectric Debye signal is not associated with shear stress relaxations on the molecular level.57,58 Therefore, there are a number of experimental observations which suggest that the time scales involved in viscous ow are associated with the process rather than the Debye type dielectric peak. Although considered in the literature,39,41 the fact that the dielectric peak contributes only a few percent to the entire relaxation strength does not imply that only a fraction of molecules participate in the process of viscous ow. The more pronounced separation between the Debye relaxation and the -process in 2M1B and 2E1H favors an unambiguous assignment of one of the peaks to structural relaxation by evaluating the relation between viscosity and relaxation time . Figure 5 compares dielectric relaxation times, D and , of 2-methyl-1-butanol with viscosity data taken from the literature.59,60 There are two routes to relating viscosity and orientational correlation times. One widely used expression is the hydrodynamic approach known as Stokes-Einstein-Debye equation61,62 1 k BT , 6V 3

where k B is the Boltzmann constant, is the rank of the orientational correlation function considered ( 1 for dipole relaxation , and V is the hydrodynamic volume of the spherical object of interest. Alternatively, the Maxwell model predicts G , 4

where G is the slightly temperature dependent innite frequency shear modulus. In the viscous regime of a liquid, the variation of with temperature greatly exceeds the concomitant changes of k B T/V or G . 63 In practice, the 16 decade change of relaxation times between 100 s at T g and phonon frequencies translates into a 17 order of magnitude change of the viscosity for many substances.64 Adopting this relation in Fig. 5 together with a value of log10 G (T g )/Pa 9.4 equivalent to (T g ) 2.5 1012 P] leads to an excellent agreement between the viscosity of 2M1B and the VFT extrapolation of the -relaxation times. In order to align the viscosity data with the Debye times D , a value of log10 G (T g )/Pa 6.7 would be required, which is remote from any typical innite frequency shear modulus for such systems. For example, liquids such as glycerol, 1,3butanediol, and 2-methyl-2,4-pentanediol exhibit the typical values for G in the range of 0.33 GPa.65,66 As a consequence of the Debye process being much slower than the dielectric relaxation and mechanical time scales, shear stresses and viscous ow processes have already equilibrated on the time scale of the Debye mode and the Debye peak should not be regarded a signature of larger scale structural relaxation. There are further features that discriminate the behavior of the dielectric Debye peak from the typical phenomenology of structural relaxation dynamics. The dielectric results of the three liquids studied here, 2M1B, 2E1H, and DM1O, indicate that the spectral difference between D and near 14 2000) than previously T g covers a larger range ( D / observed. Interestingly, these different separations between Debye and -peak frequency do not persist at higher temperatures and accordingly faster dynamics. This is seen in Fig. 4, where this spectral offset approaches a common value of D / 100 in the high temperature limit. Because the present experimental data are limited in frequency to 10 MHz, the high temperature ratio of 100 can be derived only from extrapolation. However, dielectric experiments performed at microwave frequencies support this trend,43,44,67,68 as shown by results for methanol and dodecanol which are included in Fig. 4. Molecular simulations also indicate two dielectric processes in the high frequency regime, separated by approximately two orders of magnitude in frequency.69,70 Furthermore, a similar offset is seen in a comparison between the dielectric Debye peak and ultrasonic and hypersonic responses in propanol and pentanol.71 As a consequence of the D / 100 observation, the frequency of the Debye process will not exceed values around 1010 1011 Hz in the T limit, whereas structural relaxation reaches phonon frequencies of order 1013 Hz. We consider this yet another signature of the Debye process being decoupled from the modes involved in structural relaxation. Still, the Debye relaxation time D(T) parallels the temperature dependence of both (T) and (T), especially in the regime of lower viscosity and faster dynamics. To further investigate if other properties of the Debye processes deviate from the typical behavior of primary relaxation processes, we analyze the dielectric relaxation strength of the alcohols in Fig. 6. Using the peak frequency as abscissa scale is motivated by an observation made by

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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004

Dynamics of glass-forming liquids. IX


FIG. 6. Dielectric relaxation strength of the prominent Debye peak ( D , open symbols and of the process ( , solid symbols normalized to their values at T g for a series of alcohols as a function of peak frequency . The Debye peak results display a common trend towards a relaxation strength of zero as the peak frequency approaches the high temperature limit at 1010 1011 Hz, while the relaxation results follow a different trend towards 1013 Hz in the high temperature limit. Data for 1-propanol are taken from Ref. 24, 5-methyl-2-hexanol data are from Ref. 39, and the results for propylene carbonate are from Ref. 72. Note that the different peaks (D 1 ) for the same liquid, 2-methyl-1-butanol, follow different ( )/ (T g ) paths.

Schonhals, which states that the dielectric amplitude versus peak frequency of the relaxation of simple supercooled liquids display a rather characteristic kink,72 indicative of the change in the dynamical behavior at a temperature denoted T B . 52,73 For all the Debye peaks of the alcohols open symbols in Fig. 6 , the dielectric strength values normalized to their values at T g ) seem to approach zero within a narrow range of around 1010 1011 Hz. In order to show the typical concomitant behavior of the dielectric peak of a nonassociating liquid, Fig. 6 includes data on propylene carbonate taken from the work of Schonhals.72 In this graph, the case of 2-methyl-1-butanol is of particular interest, because we data for the two distinct dielectric peaks have obtained curve for the Debye of the same sample. While the peak open circles follows the common trend of other Debye processes, the small but spectrally separate peak of 2M1B solid circles matches the characteristic behavior of structural relaxation in a nonassociating glass former. The challenge that remains is to nd a model that is consistent with the observed features discussed above. Among the various models that have been proposed, one picture put forward by Floriano and Angell has made clustering in terms of self-micellization responsible for the prominent Debye character of the dielectric response of alcohols.74 Dielectric losses originating from small amounts ( 1 wt %) of alcohol as dielectric probes in glass-forming alkanes also occur at frequencies well below those of the structural relaxation, albeit without Debye character.75,76 The analysis of the effective dipole moments and sizes of these dielectric probes is indicative of clusters of alcohol molecules within which the molecular dipole moments tend to cancel. Also supportive of this view is the amount of alkane

that can be added to alcohol before the prominent dielectric peak begins to lose the Debye character,44 consistent with the idea that polar and nonpolar moieties are spatially separated by micellization. Reverse micellar structures of the momohydroxy alcohols with intramicellar polar groups held together by hydrogen bonds and the nonpolar alkyl groups pointing outward could be energetically favorable structures, based on the same forces that drive the formation of waterin-oil type microemulsions.7779 In this case, the alcohol molecules play the role of surfactants, which easily explains why diols, polyols, and monohydric cases with sufcient steric hindrance will not form such structures. In case the Debye peak is associated with the rotation of the entire cluster, it is not at all clear why these micelles with presumably very different sizes e.g., 1-propanol versus 3,7-dimethyl-1octanol should rotate on similar time scales at a given vis100. cosity, as suggested by the constant ratio of D / Within such a picture the peak could originate from the alkyl group motion, where some coupling with -OH motion leads to moderate values for the dielectric strength . Note that typical values of glass-forming alkanes are only around 0.01 or smaller.75 For example, 2-methyl-1-butanol at 1, while its nonasits T g 125 K displays a value of sociating isomer sec-butyl-methyl-ether with similar dipole moment has a value of 12 at T g 97 K. 80 Therefore, the relaxation amplitude of the modes which are active on the time scale of the structural relaxation are too small to agree with individual molecular dipoles, while the intensity of the Debye peak is much larger than expected and a Kirkwood dipole correlation factor g larger than unity is commonly invoked to explain these large D values. As an alternative for future consideration, proton conductivity within reverse micelles could also be made responsible for the dielectric amplication or enhancement based on the Maxwell-Wagner-Sillars theory of heterogeneous dielectrics.27,81 According to this theory and its experimental justications,82,83 the mixing of a conductive ller into a nonpolar matrix generates a Debye peak, because charge carrier motion becomes spatially limited. The position of the Debye peak will depend on the diffusivity of the charges and is thereby likely to display the temperature dependence of the surrounding dynamics. The attractive feature of such a view is that it would explain why the prominent dielectric peak posesses no mechanical or calorimetric counterpart.

Three glass-forming alcohols, 2-methyl-1-butanol, 2-ethyl-1-hexanol, and 3,7-dimethyl-1-octanol, have been studied across ten decades in relaxation time regarding their dielectric behavior. Analogous to a number of other monohydroxy alcohols, these liquids feature three distinct dielectric peaks: the large Debye type D peak, a faster and much smaller asymmetrically broadened process , and an even smaller and faster symmetrically broadened secondary relaxation of the Johari-Goldstein type. While the and relaxations contribute only several percent towards the total dielectric relaxation strength, their entire behavior parallels the and peaks of other nonassociating liquids. Based on the current and previous results, a variety of dielectric to

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J. Chem. Phys., Vol. 121, No. 22, 8 December 2004


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mechanical relaxation time ratios are observed in the viscous regime ( D / 14 2000), while a universal value of 100 for that ratio appears to evolve in the high temperature limit. In contrast to typical structural relaxation modes, the Debye peak fails to approach phonon frequencies in the limit of high temperatures, but rather approaches limiting peak frequencies around 1010 1011 Hz. Additionally, the pattern with which the dielectric amplitude of the Debye peak approaches zero in the T limit is shown to differ qualitatively from the typical trend seen for structural relaxations in both monohydroxy alcohols and simple liquids. In support of earlier observations, this work increases the amount of evidence that the processes of viscous ow, mechanical shear stress relaxation, density-density correlations, and heat capacity contributions all occur on time scales that are distinctly faster than those of the dielectric Debye signal. The decoupling of the main dielectric from the structural modes in many monohydroxy alcohols needs to be accounted for in our future understanding of the complex dielectric behavior of these important liquids.
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