Discovering connections between Terahertz vibrations and ... · 2 Terahertz vibrational modes (<...
9
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015 S1 Electronic Supplementary Information (ESI) Discovering connections between Terahertz vibrations and elasticity underpinning the collective dynamics of the HKUST-1 metal-organic framework Matthew R. Ryder, a,b Bartolomeo Civalleri, c Gianfelice Cinque b and Jin-Chong Tan a, * a Department of Engineering Science, University of Oxford, Parks Road, Oxford OX1 3PJ, UK b Diamond Light Source, Harwell Campus, Didcot, Oxford OX11 0DE, UK c Department of Chemistry, NIS and INSTM Reference Centre, University of Turin, via P. Giuria 7, 10125 Torino, Italy *[email protected] Table of Contents 1 HKUST-1 Lattice Parameters 2 2 Terahertz vibrational modes (< 600 cm -1 ) of HKUST-1 3 2.1 IR active modes 3 2.2 Raman active modes 4 2.3 Non-optically active modes 5 3 Animations (movie clips) of THz collective lattice vibrations computed from ab initio density functional theory (DFT) 7 3.1 Low energy collective vibrations at 2.4 THz (81 cm -1 ) 7 3.2 Low energy collective vibrations at 1.7 THz (58 cm -1 ) 7 3.3 Low energy collective vibrations at 0.5 THz (16 cm -1 ) 8 4 Visualisation of all DFT calculated modes (0 – 3226 cm -1 ) 9 Electronic Supplementary Material (ESI) for CrystEngComm. This journal is © The Royal Society of Chemistry 2016
Transcript of Discovering connections between Terahertz vibrations and ... · 2 Terahertz vibrational modes (<...
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S1
Electronic Supplementary Information (ESI)
Discovering connections between Terahertz vibrations and elasticity underpinning the collective dynamics of the HKUST-1 metal-organic framework
Matthew R. Ryder,a,b Bartolomeo Civalleri,c Gianfelice Cinqueb and Jin-Chong
Tana,*
a Department of Engineering Science, University of Oxford, Parks Road, Oxford OX1 3PJ, UK
b Diamond Light Source, Harwell Campus, Didcot, Oxford OX11 0DE, UK c Department of Chemistry, NIS and INSTM Reference Centre, University of Turin,
via P. Giuria 7, 10125 Torino, Italy
Table of Contents
1 HKUST-1 Lattice Parameters 2
2 Terahertz vibrational modes (< 600 cm-1) of HKUST-1 3
2.1 IR active modes 3
2.2Raman active modes 4
2.3Non-optically active modes 5
3 Animations (movie clips) of THz collective lattice vibrations computed from
ab initio density functional theory (DFT) 7
3.1 Low energy collective vibrations at 2.4 THz (81 cm-1) 7
3.2 Low energy collective vibrations at 1.7 THz (58 cm-1) 7
3.3 Low energy collective vibrations at 0.5 THz (16 cm-1) 8
4 Visualisation of all DFT calculated modes (0 – 3226 cm-1) 9
Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2016
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S2
1 HKUST-1 Lattice Parameters
HKUST-1(Fm-3m)
Method Latticeparameters(Å) Volume(Å3)a
Experimental* 26.304 691.90B3LYP 26.327 693.11B3LYP-D 26.296 691.48
• B3LYPerrorinlatticeparameters:0.09%• B3LYP-Derrorinlatticeparameters:0.03%
*LocalVibrationalMechanismforNegativeThermalExpansion:ACombinedNeutronScatteringandFirst-PrinciplesStudyANGEWANDTECHEMIEINTERNATIONALEDITIONVolume49,Issue3,January12,2010,Pages:585–588,VanessaK.Peterson,GordonJ.Kearley,YueWu,AnibalJavierRamirez-Cuesta,EwoutKemnerandCameronJ.Kepert
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S3
2 Terahertz vibrational modes (< 600 cm-1) of HKUST-1 2.1 IR active modes
Mode(cm-1)
IRREP Description
81.47 F1u OrganicLinkerTrampoline-likeMotion138.88 F1u PaddleWheelRockingwithOrganicLinkerRocking
142.91 F1u PaddleWheelDeformation(Cu-CuBuckling)andTranslationwithLinkerRocking
192.76 F1u OrganicLinkerRocking 250.10 F1u PaddleWheelDeformation(StrongCu-CuBuckling) 288.99 F1u PaddleWheelDeformation(O-Cu-OBendingandCu-CuBuckling) 294.17 F1u AsymmetricCu-OStretching-PaddleWheelDeformation(O-Cu-O
Bending) 303.05 F1u 344.19 F1u PaddleWheelDeformationwithLinkerRocking 500.18 F1u OPAromaticRingDeformation
527.83 F1u IPAromaticRingDeformationwithPartiallySymmetricCu-OStretching
550.42 F1u PartiallySymmetricCu-OStretching(Symmetricwithrespecttoeachcarboxylgroup)
IRREP=Irreduciblerepresentation;IP=in-plane;OP=out-of-plane
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S4
2.2 Raman active modes
Mode(cm-1)
IRREP Description
58.07 F2g StrongPaddleWheelRotationwithOrganicLinkerTrampoline-likeMotion
98.41 Ag OrganicLinkerTrampoline-likeMotion(SymmetricClusterBreathing)
112.40 Eg StrongPaddleWheelDeformationandSwelling/Breathing 133.33 F2g AsymmetricPaddleWheelDeformationwithOrganicLinker
Rocking138.93 F2g 150.91 Eg PaddleWheelRocking158.92 F2g 176.25 Eg OrganicLinkerRocking198.81 F2g 214.35 Eg PaddleWheelSwelling/Breathing(Cu-CuStretching)215.10 Ag 263.44 Eg AsymmetricPaddleWheelDeformation(O-Cu-OBending)
269.24 F2g AsymmetricPaddleWheelDeformation(O-Cu-OBendingandCu-CuRocking)
294.91 Eg SymmetricCu-OStretching-PaddleWheelSwelling/Breathing(O-Cu-OBending)withLinkerRocking297.00 F2g
303.36 Ag SymmetricCu-OStretching-PaddleWheelSwelling/Breathing(O-Cu-OBending)
316.02 F2g PaddleWheelDeformationwithLinkerRocking322.83 Eg
475.16 F2g IPAromaticRingDeformationwithPartiallySymmetricCu-OStretching
499.81 F2g OPAromaticRingDeformation503.05 Eg 519.49 Eg IPAromaticRingDeformationwithSymmetricCu-O
Stretching524.80 F2g
537.82 Ag SymmetricCu-OStretching(PaddleWheelSwelling/Breathing)
IRREP=Irreduciblerepresentation;IP=in-plane;OP=out-of-plane
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S5
2.3 Non-optically active modes
Mode(cm-1)
IRREP Description
16.32 F2u StrongPaddleWheelDeformationandTranslationalMotion(SymmetricClusterRotation)
20.43 Eu StrongPaddleWheelDeformationandTranslationalMotion
63.17 F2u PaddleWheelDeformationandTranslationalMotionwithOrganicLinkerRotating
78.28 Bg PaddleWheelDeformationwithOrganicLinkerRotating(SymmetricClusterRocking)
79.66 Au PaddleWheelDeformationwithOrganicLinkerRotating 81.72 F1g PaddleWheelDeformationandRotationwithOrganicLinker
Rocking84.54 F1g 94.15 Bu OrganicLinkerTrampoline-likeMotion 102.09 Eu
StrongAsymmetricPaddleWheelDeformationandRotation103.01 F2u 107.99 Au 118.29 F1g
137.97 Bg PaddleWheelRockingwithOrganicLinkerRocking(SymmetricClusterRocking)
139.94 F1g PaddleWheelRockingwithOrganicLinkerRocking 141.64 F2u 160.95 F1g PaddleWheelDeformation 170.78 Eu OrganicLinkerRocking 174.88 Bu PaddleWheelTranslationalMotion
191.10 F2u AsymmetricPaddleWheelDeformation(Cu-CuBuckling)withLinkerRocking
194.69 Eu AsymmetricPaddleWheelDeformation(O-Cu-OBending) 215.91 F1g PaddleWheelRotationwithStrongLinkerRocking
239.39 F2u PaddleWheelDeformation(StrongCu-CuBuckling)withLinkerRocking
262.09 F1g AsymmetricPaddleWheelDeformation(O-Cu-OBending) 268.62 Bg
270.22 F1g AsymmetricPaddleWheelDeformation(O-Cu-OBendingandCu-CuRocking)
274.07 F2u AsymmetricPaddleWheelDeformation(O-Cu-OBendingandCu-CuBuckling)
281.69 Eu 298.14 Bu 300.70 F2u
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S6
303.88 F1g PaddleWheelDeformationwithLinkerRocking317.89 Eu
330.41 F2u 412.51 Au
IPAromaticRingRotationwithAsymmetricCu-OStretching441.34 F2u 456.51 Bg 456.68 F1g
476.25 F1g IPAromaticRingDeformationwithPartiallySymmetricCu-OStretching
492.60 F1g OPAromaticRingDeformation498.36 F2u
499.94 Eu 519.46 Eu IPAromaticRingDeformationwithPartiallySymmetricCu-O
Stretching523.70 F2u
552.23 Bu PartiallySymmetricCu-OStretching(Symmetricwithrespecttoeachcarboxylgroup)
590.28 Eu FullyAsymmetricCu-OStretching(Asymmetricwithrespecttoeachcarboxylgroup)
IRREP=Irreduciblerepresentation;IP=in-plane;OP=out-of-plane
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S7
3 Animations (movie clips) of THz collective lattice vibrations computed from ab initio density functional theory (DFT)
3.1 Low energy collective vibrations at 2.4 THz (81 cm-1)
Views down the <111> and <110> directions, showing a ‘trampoline-like’ motion linked to negative thermal expansion (NTE). Movie clips URLs <111> (Left panel): http://www.eng.ox.ac.uk/tan/thz-anim/hkust1_trampoline_81-47_111 <110> (Right panel): http://www.eng.ox.ac.uk/tan/thz-anim/hkust1_trampoline_81-47_110
3.2 Low energy collective vibrations at 1.7 THz (58 cm-1)
Views down the <110> and <011> directions, showing a molecular rotor motion of the Cu-based paddle-wheel moiety. Movie clips URLs <110> (Left): http://www.eng.ox.ac.uk/tan/thz-anim/hkust1_rotor_58-07_110 <011> (Right): http://www.eng.ox.ac.uk/tan/thz-anim/hkust1_rotor_58-07_011
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S8
3.3 Low energy collective vibrations at 0.5 THz (16 cm-1)
Viewed down the <100> and <110> directions, showing a cluster rotation mechanism, which is potentially linked to auxeticity (negative Poisson’s ratio). Movie clips URLs <100> (Left): http://www.eng.ox.ac.uk/tan/thz-anim/hkust1_cluster_16-32_100_ <110> (Right): http://www.eng.ox.ac.uk/tan/thz-anim/hkust1_cluster_16-32_110
CrystEngComm New Talent / ESI / Ryder et al. 19 Jan 2015
S9
4 Visualisation of all DFT calculated modes (0 – 3226 cm-1) Link to animation hosted at University of Torino: http://www.crystal.unito.it/vibs/hkust%2D1/ IMPORTANT: This animation requires latest version of Java to be unblocked and fully functional on the Firefox (Win/OSX) and Safari (OSX) browsers. It may not be compatible with other browsers.
