fullerÉnek És szÉn nanocsÖvek
DESCRIPTION
FULLERÉNEK ÉS SZÉN NANOCSÖVEK. előadás fizikus és vegyész hallgatóknak ( 2008 tavaszi félév – május 07.) Kürti Jenő ELTE Biológiai Fizika Tanszék e-mail: [email protected]: virag.elte.hu/kurti. G. Kresse et al. FIRST PRINCIPLES CALCULATIONS DFT: LDA - PowerPoint PPT PresentationTRANSCRIPT
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FULLERÉNEK ÉS
SZÉN NANOCSÖVEK
előadás fizikus és vegyész hallgatóknak
(2008 tavaszi félév – május 07.)
Kürti Jenő
ELTE Biológiai Fizika Tanszék
e-mail: [email protected] www: virag.elte.hu/kurti
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FIRST PRINCIPLES CALCULATIONSFIRST PRINCIPLES CALCULATIONS
DFT: LDA
plane wave basis set, cutoff: 400 eV
G. Kresse et al
Wien
Budapest
Lancaster
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arrangement: tetragonal (hexagonal for test)
distance between tubes: l = 0.6 nm (1.3 nm for test)
hexa
tetra
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r1
r2r3
1
23
bond lengths
bond angles
(4,2)
d
c
56 atoms
building block
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tube axis
ideal hexagonal lattice
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tube axis
d increases
c decreases
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tube axis
extra bond misalignment
1
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GEOMETRY OPTIMIZATION
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diameter
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1/d vs 1/d0
DFT optimized diameter
1/d0 (nm-1)
1/d
(nm
-1)
.
ZZ
AC
CH
r0 = 0.1413 nm
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(d-d0)/d0 vs 1/d0
relative change
1/d0 (nm-1)
(d-d
0)/d
0 (
%)
.
ZZ
AC
CH
r0 = 0.1413 nm
(9,0) : 1.06 ± 0.01 %
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(d-d0)/d0 vs 1/d0
relative change
1/d0 (nm-1)
(d-d
0)/d
0 (
%)
.
ZZ
AC
CH
r0 = 0.1413 nm
(9,0) : 1.06 ± 0.01 %
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length of the unit cell
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unit cell lengths vs 1/d0
relative change
1/d0 (nm-1)
(c-c
0)/c
0 (
%)
.
ZZ
AC
CH
r0 = 0.1413 nm
ZZ triads
(9,0) : -0.05 ± 0.01 %
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bond lengths
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(r1-r0)/r0 vs 1/drelative change
1/d (nm-1)
(r1-
r 0)/r
0 (
%)
.
ZZ
AC
CH
r0 = 0.1413 nm
ZZ triads
(9,0) : -0.32 ± 0.004 %
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(r2-r0)/r0 vs 1/drelative change
1/d (nm-1)
(r2-
r 0)/r
0 (
%)
.
ZZ
AC
CH
r0 = 0.1413 nm
ZZ triads
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bond angles
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bond angle 1 vs 1/d0
DFT optimized
1/d0 (nm-1)
1 (
deg)
.
ZZ
AC
CH
r0 = 0.1413 nm
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pyramidalization or rehybridization
sp2 sp3
S.Niyogi et al., Acc. Chem. Res. 35, 1105 (2002)
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pyramidalization angle P vs 1/d0
DFT optimized
1/d0 (nm-1)
P (
deg)
.
ZZ
AC
CH
r0 = 0.1413 nm
C60: 11.6°
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BAND STRUCTURE
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tight binding(nearest neighbour)
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DFT (VASP)
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(6,5) - DFT
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(20,0)
zigzag
chiral
(19,0)(17,0)(16,0)
(14,0)(13,0)
(11,0)
(10,0)
(8,0)
(7,0)(5,0)(4,0)
(6,4)
(6,2)
(5,3)
(6,1)
(4,3)
(5,1)(4,2)
(3,2)
ZF-TB
DFT
1/d
1/d
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(5,0)
ZF-TB: Eg = 2.3 eV
DFT: Eg = 0 !
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(20,0)
zigzag
chiral
(19,0)(17,0)(16,0)
(14,0)(13,0)
(11,0)
(10,0)
(8,0)
(7,0)(5,0)(4,0)
(6,4)
(6,2)
(5,3)
(6,1)
(4,3)
(5,1)(4,2)
(3,2)
ZF-TB
DFT
1/d
1/d
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ZF-TB METALLIC
non-armchair: zigzag, chiral
kF
kF kF - kF (d)
= f(1/d2)
K tube axis
opening of a secondary gap
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secondary gap in (7,1)
0.14 eV
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ZF-TB METALLIC
armchair
kF kF - kF (d)
= f(1/d2)
K
kF
tube axis
NO secondary gap
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(6,6)
(4,4)
kF (d)=2/3
kF
kFF
F
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AC
(3,3)
(4,4)
(5,5)
(6,6)
(7,7)(8,8)
(9,9)(10,10)
(11,11)
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9 0 36 0 0.7010 0.7084 -0.043 330.3 317.8 318.2
8 2 56 10.9 0.7139 0.7209 -0.021 324.6 316.5 314.9
7 4 124 21.1 0.7512 0.7580 -0.051 308.7 307.1 303.7
10 0 40 0 0.7789 0.7852 0.008 298.0 294.5 290.7
6 6 24 30 0.8095 0.8158 -0.058 286.8 284.3 283.6
11 0 44 0 0.8568 0.8629 -0.051 271.2 268.2 264.6
12 0 48 0 0.9347 0.9401 -0.013 248.9 242.8 242.2
7 7 28 30 0.9444 0.9499 -0.053 246.3 246.2 243.4
13 0 52 0 1.0126 1.0172 0.006 230.0 228.9 225.5
8 8 32 30 1.0793 1.0843 -0.046 215.8 216.5 213.1
14 0 56 0 1.0905 1.0951 -0.026 213.7 212.4 209.7
15 0 60 0 1.1684 1.1725 -0.007 199.6 196.4 195.6
9 9 36 30 1.2142 1.2186 -0.037 192.0 192.7 189.4
16 0 64 0 1.2463 1.2501 0.002 187.2 186.4 183.7
17 0 68 0 1.3241 1.3281 -0.023 176.2 175.6 173.0
10 10 40 30 1.3491 1.3531 -0.031 172.9 173.6 170.7
18 0 72 0 1.4020 1.4054 -0.005 166.5 164.4 163.5
19 0 76 0 1.4799 1.4831 0.001 157.8 157.3 155.1
11 11 44 30 1.4840 1.4874 -0.024 157.3 158.0 155.2
20 0 80 0 1.5578 1.5613 -0.019 149.9 149.3 147.1
4 0 16 0 0.3116 0.3341 -1.293 700.4 651.3 642.3
3 2 76 23.4 0.3395 0.3531 0.277 662.7 651.1 648.6
4 1 28 10.9 0.3569 0.3732 -0.343 627.0 589.5 584.1
5 0 20 0 0.3895 0.4043 -0.274 578.8 544.9 536.1
3 3 12 30 0.4047 0.4176 -0.096 560.3 541.1 551.4
4 2 56 19.1 0.4122 0.4252 -0.196 550.4 539.5 536.3
5 1 124 8.9 0.4337 0.4462 -0.172 524.4 487.1 493.2
6 0 24 0 0.4673 0.4793 -0.188 488.2 463.6 458.5
4 3 148 25.3 0.4738 0.4833 0.101 484.1 479.4 476.0
5 2 52 16.1 0.4864 0.4970 -0.063 470.8 451.5 448.8
6 1 172 7.6 0.5108 0.5216 -0.192 448.6 437.8 432.8
4 4 16 30 0.5396 0.5489 -0.028 426.3 424.3 419.2
5 3 196 21.8 0.5452 0.5546 -0.084 421.9 417.4 413.5
7 0 28 0 0.5452 0.5546 -0.043 421.9 411.0 405.3
6 2 104 13.9 0.5617 0.5704 -0.008 410.3 404.5 400.2
7 1 76 6.6 0.5881 0.5971 -0.090 391.9 374.6 373.1
6 3 84 19.1 0.6182 0.6263 -0.038 373.6 364.5 363.1
8 0 32 0 0.6231 0.6319 -0.119 370.3 363.6 358.5
5 5 20 30 0.6746 0.6821 -0.058 343.1 337.3 338.9
6 4 152 23.4 0.6790 0.6864 -0.043 340.9 336.1 333.4
n m N Θ0 d0 dDFT c/c0 234/dDFT DFT *DFT n m N Θ0 d0 dDFT c/c0 234/dDFT DFT *
DFT
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REZGÉSI TULAJDONSÁGOK
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D band
Radial Breathing Mode
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(5,3)
quadratic fit force constant RBM-frequency
DFT
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RBM vs 1/d0
1/d0 (nm-1)
(c
m-1)
linear fit for large diameters
Alarge_d= 233.1
ZZ
AC
CH
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RBM vs 1/ddeviation from linear fit
1/d (nm-1)
(
cm-1)
ZZ
AC
CH
7,0
5,3
d=0.5546 nm
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ZZ
AC
CH
AZZ= 232
AAC= 236
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COUPLING of
TOTALLY SYMMETRIC MODES
(RBM + G (HFM))
radial tangential
1 for achiral
2 for chiral
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ZZ
AC
CH
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Raman
Stokes: 2 = 1 –
(Anti-Stokes: 2 = 1 +
1
1
2 = 1 –
ba
2 = 1 +
1
1
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hin hin hout houthout hin
(incoming) resonance RamanC. V. Raman
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(a) RBM spectra of HiPCO produced carbon nanotubes at different excitation energies.
The spectra are vertically offset for clarity. From top to bottom the laser energy increases between 1.51 and 1.75 eV. Each peak arises from a different (n,m) nanotube.
(b) Resonance profiles for the peaks marked in a by vertical lines. The dots are experimental data; the lines are fits.
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Two-dimensional plot of the radial-breathing-mode range vs. laser excitation energy. Note the various laola-like resonance enhancements, from which we can determine both the optical transition energies and the approximate diameter of the nanotubes. The spectra were each calibrated against the Raman spectrum of CCl4.
2D RBM
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Contour plot of 2D RBM
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Contour plot of 2D RBM
A. Jorio et al., (in press)