title: The glass transition in high-density amorphous ice.
abstract: There has been a long controversy regarding the glass transition in low-density amorphous ice (LDA). The central question is whether or not it transforms to an ultraviscous liquid state above 136 K at ambient pressure prior to crystallization. Currently, the most widespread interpretation of the experimental findings is in terms of a transformation to a superstrong liquid above 136 K. In the last decade some work has also been devoted to the study of the glass transition in high-density amorphous ice (HDA) which is in the focus of the present review. At ambient pressure HDA is metastable against both ice I and LDA, whereas at > 0.2 GPa HDA is no longer metastable against LDA, but merely against high-pressure forms of crystalline ice. The first experimental observation interpreted as the glass transition of HDA was made using in situ methods by Mishima, who reported a glass transition temperature Tgof 160 K at 0.40 GPa. Soon thereafter Andersson and Inaba reported a much lower glass transition temperature of 122 K at 1.0 GPa. Based on the pressure dependence of HDA's Tgmeasured in Innsbruck, we suggest that they were in fact probing the distinct glass transition of very high-density amorphous ice (VHDA). Very recently the glass transition in HDA was also observed at ambient pressure at 116 K. That is, LDA and HDA show two distinct glass transitions, clearly separated by about 20 K at ambient pressure. In summary, this suggests that three glass transition lines can be defined in the p-T plane for LDA, HDA, and VHDA.
authors: Institute of Physical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
authors: Thomas
authors: T
authors: Loerting
authors: Institute of Physical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
authors: Violeta
authors: V
authors: Fuentes-Landete
authors: Institute of Physical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
authors: Philip H
authors: PH
authors: Handle
authors: Institute of Physical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
authors: Markus
authors: M
authors: Seidl
authors: Institute of Physical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
authors: Katrin
authors: K
authors: Amann-Winkel
authors: Fakultät Physik, Technische Universität Dortmund, Otto-Hahn-Straße 4, D-44221 Dortmund, Germany.
authors: Catalin
authors: C
authors: Gainaru
authors: Fakultät Physik, Technische Universität Dortmund, Otto-Hahn-Straße 4, D-44221 Dortmund, Germany.
authors: Roland
authors: R
authors: Böhmer
keywords: Dielectric relaxation spectroscopy; Differential scanning calorimetry; Glass transition; High-density amorphous ice; Polyamorphism
references: Phys Rev Lett. 2004 Nov 19;93(21):215703
references: 15601032
references: Phys Chem Chem Phys. 2006 Jan 21;8(3):386-97
references: 16482282
references: J Chem Phys. 2011 Feb 14;134(6):064507
references: 21322705
references: Proc Natl Acad Sci U S A. 2013 Oct 29;110(44):17720-5
references: 24101518
references: Nature. 2014 Jun 19;510(7505):381-4
references: 24943953
references: Chem Rev. 2002 Aug;102(8):2627-50
references: 12175262
references: Phys Chem Chem Phys. 2012 Dec 21;14(47):16386-91
references: 23132426
references: Sci Rep. 2012;2:390
references: 22550566
references: Phys Rev Lett. 2002 Jun 3;88(22):225503
references: 12059427
references: Phys Chem Chem Phys. 2012 Aug 14;14(30):10595-602
references: 22752009
references: J Phys Chem B. 2006 Jun 15;110(23):11033-6
references: 16771359
references: J Chem Phys. 2006 Sep 7;125(9):094501
references: 16965091
references: J Chem Phys. 2014 Mar 21;140(11):114504
references: 24655190
references: Phys Rev Lett. 2014 Apr 11;112(14):145701
references: 24765988
references: Phys Chem Chem Phys. 2011 May 21;13(19):8783-94
references: 21431195
references: Phys Rev Lett. 2005 Dec 2;95(23):235702
references: 16384318
references: Phys Chem Chem Phys. 2005 Apr 7;7(7):1423-31
references: 19787964
references: Phys Rev Lett. 2013 Feb 8;110(6):065701
references: 23432275
references: Proc Natl Acad Sci U S A. 2005 Nov 15;102(46):16558-62
references: 16267132
references: Science. 1991 Oct 18;254(5030):406-8
references: 17742228
references: J Chem Phys. 2013 Nov 14;139(18):184504
references: 24320281
references: Science. 2008 Feb 1;319(5863):582-7
references: 18239117
references: J Chem Phys. 2012 Dec 28;137(24):244506
references: 23277944
references: Phys Rev Lett. 2005 Nov 11;95(20):205503
references: 16384070
references: J Chem Phys. 2013 Feb 14;138(6):064509
references: 23425481
references: Proc Natl Acad Sci U S A. 2014 Jul 1;111(26):9413-8
references: 24858957
references: J Chem Phys. 2006 Aug 21;125(7):074505
references: 16942349
references: Proc Natl Acad Sci U S A. 2014 Jul 1;111(26):9374-5
references: 24951509
references: Phys Rev Lett. 2000 Nov 6;85(19):4100-3
references: 11056634
references: Phys Chem Chem Phys. 2010 Jan 21;12(3):708-12
references: 20066356
references: Phys Rev Lett. 2006 Jan 20;96(2):025702
references: 16486598
references: Science. 2004 Oct 29;306(5697):820-1
references: 15514145
references: J Chem Phys. 2011 Sep 14;135(10):104504
references: 21932907
references: J Chem Phys. 2012 Jan 14;136(2):026101
references: 22260617
references: Phys Rev Lett. 2000 May 1;84(18):4112-5
references: 10990623
references: J Phys Chem B. 2011 Dec 8;115(48):14141-8
references: 21793514
references: Annu Rev Phys Chem. 2004;55:559-83
references: 15117262
references: J Chem Phys. 2004 Aug 15;121(7):3161-4
references: 15291626
references: J Chem Phys. 2006 Jun 14;124(22):224503
references: 16784294
references: Phys Rev Lett. 2005 Mar 18;94(10):107803
references: 15783525
references: J Chem Phys. 2006 Nov 21;125(19):194502
references: 17129118
references: J Chem Phys. 2014 Apr 7;140(13):134504
references: 24712798
references: J Chem Phys. 2008 Jan 28;128(4):044510
references: 18247972
references: Proc Natl Acad Sci U S A. 2014 Dec 9;111(49):17402-7
references: 25422420
references: Phys Chem Chem Phys. 2005 Sep 7;7(17):3210-20
references: 16240034
references: Proc Natl Acad Sci U S A. 2011 Jul 5;108(27):11013-6
references: 21690361
references: Science. 1975 Sep 12;189(4206):880-1
references: 17812529
references: J Phys Chem B. 2011 Dec 8;115(48):14167-75
references: 21879742
references: Phys Rev Lett. 2002 Nov 11;89(20):205503
references: 12443486
references: Phys Chem Chem Phys. 2014 Aug 14;16(30):16013-20
references: 24963740
references: J Chem Phys. 2005 Apr 1;122(13):134501
references: 15847475
references: Phys Rev Lett. 2004 Jun 4;92(22):225702
references: 15245238
references: Phys Chem Chem Phys. 2013 Jan 14;15(2):576-80
references: 23183587
references: Phys Rev Lett. 2000 Oct 9;85(15):3185-8
references: 11019297
references: J Chem Phys. 2009 Sep 21;131(11):114502
references: 19778124
references: J Phys Chem B. 2005 Nov 24;109(46):21879-83
references: 16853842
references: Phys Rev Lett. 2012 Jun 1;108(22):225901
references: 23003624
references: Phys Chem Chem Phys. 2008 Nov 7;10(41):6313-24
references: 18936855