Abstract
This article summarizes ongoing experimental efforts on nonlinear dielectric spectroscopy on plastic crystals. In plastic crystals, the relevant dipolar orientational degrees of freedom are fixed on a crystalline lattice with perfect translational symmetry. However, while they can reorient freely in the high-temperature plastic phase, they often undergo glassy freezing at low temperatures. Hence, plastic crystals are often considered as model systems for structural glass formers. It is well known that plastic crystals reveal striking similarities with phenomena of conventional supercooled liquids. However, in most cases, they can be characterized as rather strong glass formers. Nonlinear dielectric spectroscopy is an ideal tool to study glass-transition phenomena, providing insight into cooperative phenomena or hidden phase transitions, undetectable by purely linear spectroscopy. In the present article, we discuss dielectric experiments using large electric ac fields probing the nonlinear 1ω and the third-order harmonic 3ω susceptibility. In the 1ω experiments, we find striking differences compared with observations on conventional structural glass formers: at low frequencies plastic crystals do not approach the trivial response, but reveal strong additional nonlinearity. These phenomena document the importance of entropic effects in this class of glassy materials. The harmonic third-order susceptibility reveals a hump-like shape, similar to observations in canonical glass formers, indicating the importance of cooperativity dominating the glass transition. In the frequency regime of the secondary relaxations, only minor nonlinear effects can be detected, supporting arguments in favor of the non-cooperative nature of these faster dynamics processes. Based on a model by Bouchaud and Biroli, from the hump observed in the 3ω susceptibility spectra, the temperature dependence of the number of correlated particles can be determined. We document that the results in plastic crystals perfectly well scale with the results derived from measurements on conventional glass formers, providing evidence that in plastic crystals the non-Arrhenius behavior of the relaxation times also arises from a temperature dependence of the energy barriers due to growing cooperative clusters.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
R. Brand, P. Lunkenheimer, A. Loidl, J. Chem. Phys. 116, 10386 (2002)
J. Timmermans, J. Chim. Phys. 35, 331 (1938)
N.G. Parsonage, L.A.K. Staveley, Disorder in Crystals (Oxford University Press, Oxford, 1978)
J.N. Sherwood, The Plastically Crystalline State (Wiley, New York, 1979)
K. Adachi, H. Suga, S. Seki, Bull. Chem. Soc. Jpn 41, 1073 (1968)
U.T. Höchli, K. Knorr, A. Loidl, Adv. Phys. 39, 405 (1990)
A. Loidl, R. Böhmer, in Disorder Effects on Relaxational Processes, ed. by R. Richert, A. Blumen (Springer, Berlin, 1994), p. 659
M.D. Ediger, C.A. Angell, S.R. Nagel, J. Phys. Chem. 100, 13200 (1996)
H. Sillescu, J. Non-Cryst. Solids 243, 81 (1999)
M.D. Ediger, Annu. Rev. Phys. Chem. 51, 99 (2000)
P. Lunkenheimer, U. Schneider, R. Brand, A. Loidl, Contemp. Phys. 41, 15 (2000)
J.C. Dyre, Rev. Mod. Phys. 78, 953 (2006)
D.L. Leslie-Pelecky, N.O. Birge, Phys. Rev. Lett. 72, 1232 (1994)
M.A. Ramos, S. Vieira, F.J. Bermejo, J. Dawidowski, H.E. Fischer, H. Schober, M.A. González, C.K. Loong, D.L. Price, Phys. Rev. Lett. 78, 82 (1997)
R. Brand, P. Lunkenheimer, U. Schneider, A. Loidl, Phys. Rev. Lett. 82, 1951 (1999)
F. Affouard, M. Descamps, Phys. Rev. Lett. 87, 035501 (2001)
P.-J. Alarco, Y. Abu-Lebdeh, A. Abouimrane, M. Armand, Nature Mater. 3, 476 (2004)
R. Richert, J. Phys.: Condens. Matter 29, 363001 (2017)
P. Lunkenheimer, M. Michl, Th. Bauer, A. Loidl, Eur. Phys. J. Special Topics 226, 3157 (2017)
R. Richert, S. Weinstein, Phys. Rev. Lett. 97, 095703 (2006)
L.-M. Wang, R. Richert, Phys. Rev. Lett. 99, 185701 (2007)
A. Drozd-Rzoska, S.J. Rzoska, J. Zioło, Phys. Rev. E 77, 041501 (2008)
C. Crauste-Thibierge, C. Brun, F. Ladieu, D. L’Hôte, G. Biroli, J-P. Bouchaud, Phys. Rev. Lett. 104, 165703 (2010)
L.P. Singh, R. Richert, Phys. Rev. Lett. 109, 167802 (2012)
Th. Bauer, P. Lunkenheimer, S. Kastner, A. Loidl, Phys. Rev. Lett. 110, 107603 (2013)
Th. Bauer, P. Lunkenheimer, A. Loidl, Phys. Rev. Lett. 111, 225702 (2013)
S. Albert, Th. Bauer, M. Michl, G. Biroli, J.-P. Bouchaud, A. Loidl, P. Lunkenheimer, R. Tourbot, C. Wiertel-Gasquet, F. Ladieu, Science 352, 1308 (2016)
M. Michl, Th. Bauer, P. Lunkenheimer, A. Loidl, Phys. Rev. Lett. 114, 067601 (2015)
B. Riechers, K. Samwer, R. Richert, J. Chem. Phys. 142, 154504 (2015)
S. Samanta, R. Richert, J. Chem. Phys. 142, 044504 (2015)
M. Michl, Th. Bauer, P. Lunkenheimer, A. Loidl, J. Chem. Phys. 144, 114506 (2016)
B. Schiener, R. Böhmer, A. Loidl, R.V. Chamberlin, Science 274, 752 (1996)
S. Weinstein, R. Richert, Phys. Rev. B 75, 064302 (2007)
G.P. Johari, M. Goldstein, J. Chem. Phys. 53, 2372 (1970)
P. Lunkenheimer, A. Loidl, in Broadband Dielectric Spectroscopy, ed. by F. Kremer, A. Schönhals (Springer, Berlin, 2002), Chap. 5
J.-P. Bouchaud, G. Biroli, Phys. Rev. B 72, 064204 (2005)
M. Tarzia, G. Biroli, A. Lefèvre, J.-P. Bouchaud, J. Chem. Phys. 132, 054501 (2010)
C. Brun, F. Ladieu, D. L’Hôte, M. Tarzia, G. Biroli, J.-P. Bouchaud, Phys. Rev. B 84, 104204 (2011)
G.P. Johari, J. Chem. Phys. 138, 154503 (2013)
G.P. Johari, J. Chem. Phys. 145, 164502 (2016)
M. Winterlich, G. Diezemann, H. Zimmermann, R. Böhmer, Phys. Rev. Lett. 91, 235504 (2003)
G.P. Johari, J. Khouri, J. Chem. Phys. 137, 104502 (2012)
T.R. Kirkpatrick, P.G. Wolynes, Phys. Rev. B 36, 8552 (1987)
P.G. Debenedetti, F.H. Stillinger, Nature 310, 259 (2001)
F. Mizuno, J.-P. Belieres, N. Kuwata, A. Pradel, M. Ribes, C. A. Angell, J. Non-Cryst. Solids 352, 5147 (2006)
C.A. Angell, in Relaxation in Complex Systems, ed. by K.L. Ngai, G.B. Wright (Office of Naval Research, Washington DC, 1985), p. 3
L.C. Pardo, P. Lunkenheimer, A. Loidl, J. Chem. Phys. 124, 124911 (2006)
Th. Bauer, M. Köhler, P. Lunkenheimer, A. Loidl, C.A. Angell, J. Chem. Phys. 133, 144509 (2010)
M. Götz, Th. Bauer, P. Lunkenheimer, A. Loidl, J. Chem. Phys. 140, 094504 (2014)
P. Lunkenheimer, S. Kastner, M. Köhler, A. Loidl, Phys. Rev. E 81, 051504 (2010)
P. Lunkenheimer, M. Köhler, S. Kastner, A. Loidl, in Structural Glasses and Supercooled Liquids: Theory, Experiment, and Applications, ed. by P.G. Wolynes, V. Lubchenko (Wiley, Hoboken, 2012), Chap. 3, p. 115
C.A. Angell, W. Sichina, Ann. N.Y. Acad. Sci. 279, 53 (1976)
D.J. Plazek, K.L. Ngai, Macromolecules 24, 1222 (1991)
R. Böhmer, C.A. Angell, Phys. Rev. B 45, 10091 (1992)
A. Srinivasan, F. J. Bermejo, A. de Andrés, J. Dawidowski, J. Zúñiga, A. Criado, Phys. Rev. B 53, 8172 (1996)
R. Brand, P. Lunkenheimer, U. Schneider, A. Loidl, Phys. Rev. B 62, 8878 (2000)
C.A. Angell, J. Phys. Chem. Solids 49, 863 (1988)
R. Böhmer, C.A. Angell, in Disorder Effects on Relaxational Processes, ed. by R. Richert, A. Blumen (Springer, Berlin, 1994), p. 11
G. Adam, J.H. Gibbs, J. Chem. Phys. 43, 139 (1965)
R. Brand, P. Lunkenheimer, A. Loidl, Phys. Rev. B 56, R5713 (1997)
M. Shablakh, L.A. Dissado, R.M. Hill, J. Chem. Soc. Faraday Trans. II 79, 369 (1983)
O. Anderson, R.G. Ross, Mol. Phys. 71, 523 (1990)
H. Forsmann, O. Anderson, J. Non-Cryst, Solids 131–133, 1145 (1991)
L.P. Singh, S.S.N. Murthy, Phys. Chem. Chem. Phys. 11, 5110 (2009)
P. Lunkenheimer, A. Loidl, J. Chem. Phys. 104, 4324 (1996)
O. Yamamuro, M. Hayashi, T. Matsuo, P. Lunkenheimer, J. Chem. Phys. 119, 4775 (2003)
D.W. Davidson, R.H. Cole, J. Chem. Phys. 18, 1417 (1950)
B. Schiener, R.V. Chamberlin, G. Diezemann, R. Böhmer, J. Chem. Phys. 107, 7746 (1997)
J. Herweg, Z. Phys. 3, 36 (1920)
P. Debye, Polar Molecules (Dover Publications, New York, 1929)
J.L. Déjardin, YuP Kalmykov, Phys. Rev. E 61, 1211 (2000)
Th. Bauer, M. Michl, P. Lunkenheimer, A. Loidl, J. Non-Cryst. Solids 407, 66 (2015)
P. Kim, A.R. Young-Gonzales, R. Richert, J. Chem. Phys. 145, 064510 (2016)
S. Samanta, R. Richert, J. Phys. Chem. B 120, 7737 (2016)
R. Richert, J. Chem. Phys. 146, 064501 (2017)
P. Gadige, S. Albert, M. Michl, Th. Bauer, P. Lunkenheimer, A. Loidl, R. Tourbot, C. Wiertel-Gasquet, G. Biroli, J.-P. Bouchaud, F. Ladieu, Phys. Rev. E 96, 032611 (2017)
F.H. Stillinger, Science 267, 1935 (1995)
J.S. Harmon, M.D. Demetriou, W.L. Johnson, K. Samwer, Phys. Rev. Lett. 99, 135502 (2007)
C. Gainaru, O. Lips, A. Troshagina, R. Kahlau, A. Brodin, F. Fujara, E.A. Rössler, J. Chem. Phys. 128, 174505 (2008)
R.V. Chamberlin, Phys. Rev. Lett. 82, 2520 (1999)
K.L. Ngai, J. Phys.: Condens. Matter 15, S1107 (2003)
W. Götze, M. Sperl, Phys. Rev. Lett. 92, 105701 (2004)
K.L. Ngai, M. Paluch, J. Chem. Phys. 120, 857 (2004)
K.L. Ngai, Phys. Rev. E 57, 7346 (1998)
R.L. Leheny, S.R. Nagel, Europhys. Lett. 39, 447 (1997)
U. Schneider, R. Brand, P. Lunkenheimer, A. Loidl, Phys. Rev. Lett. 84, 5560 (2000)
K.L. Ngai, P. Lunkenheimer, C. León, U. Schneider, R. Brand, A. Loidl, J. Chem. Phys. 115, 1405 (2001)
A. Döß, M. Paluch, H. Sillescu, G. Hinze, Phys. Rev. Lett. 88, 095701 (2002)
A. Kudlik, S. Benkhof, T. Blochowicz, C. Tschirwitz, E. Rössler, J. Mol. Struct. 479, 201 (1999)
M. Beiner, H. Huth, K. Schröter, J. Non-Cryst. Solids 279, 126 (2001)
S. Samanta, R. Richert, J. Phys. Chem. B 119, 8909 (2015)
K.L. Ngai, J. Chem. Phys. 142, 114502 (2015)
S. Samanta, R. Richert, J. Chem. Phys. 140, 054503 (2014)
B. Roling, L.N. Patro, O. Burghaus, M. Gräf, Eur. Phys. J. Special Topics 226, 3095 (2017)
C. Brun, C. Crauste-Thibierge, F. Ladieu, D. L’Hôte, J. Chem. Phys. 134, 194507 (2011)
G. Diezemann, Phys. Rev. E 85, 051502 (2012)
G. Diezemann, J. Chem. Phys. 138, 12A505 (2013)
R.M. Pick, J. Chem. Phys. 140, 054508 (2014)
U. Buchenau, J. Chem. Phys. 146, 214503 (2017)
C. Gainaru, S. Kastner, F. Mayr, P. Lunkenheimer, S. Schildmann, H. J. Weber, W. Hiller, A. Loidl, R. Böhmer, Phys. Rev. Lett. 107, 118304 (2011)
C. Gainaru, R. Meier, S. Schildmann, C. Lederle, W. Hiller, E.A. Rössler, R. Böhmer, Phys. Rev. Lett. 105, 258303 (2010)
R. Böhmer, K.L. Ngai, C.A. Angell, D.J. Plazek, J. Chem. Phys. 99, 4201 (1993)
S.A. Kivelson, G. Tarjus, Nature Mater. 7, 831 (2008)
Acknowledgements
This work was supported by the Deutsche Forschungsgemeinschaft via Research Unit FOR 1394. Stimulating discussions with S. Albert, Th. Bauer, G. Biroli, U. Buchenau, G. Diezemann, G. P. Johari, F. Ladieu, K. L. Ngai, R. Richert, R. M. Pick, and K. Samwer are gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2018 Springer International Publishing AG, part of Springer Nature
About this chapter
Cite this chapter
Lunkenheimer, P., Michl, M., Loidl, A. (2018). Nonlinear Dielectric Response of Plastic Crystals. In: Richert, R. (eds) Nonlinear Dielectric Spectroscopy. Advances in Dielectrics. Springer, Cham. https://doi.org/10.1007/978-3-319-77574-6_9
Download citation
DOI: https://doi.org/10.1007/978-3-319-77574-6_9
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-77573-9
Online ISBN: 978-3-319-77574-6
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)