time-resolved raman spectroscopy...time-resolved raman spectroscopy 2013.11.14 carl-zeiss lecture 3...
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Time-resolved Raman
Spectroscopy
2013.11.14
Carl-Zeiss Lecture 3
IPHT Jena
Hiro-o HAMAGUCHI
Department of Applied Chemistry and Institute of Molecular
Science, College of Science, National Chiao Tung University,
Taiwan
「諸行無常」 Nothing can last for ever
Time and Space: When? Where?
Sun set at Shinjiko Lake. http://blogs.yahoo.co.jp/naru3075/41266684.html
Organ
Cell
Organelle
Liposome
Solvation structure
Complex
Aggregate
Molecule
Atom
Biology
Chemistry
Physics
Time Space
109 s
103 s
102 s
10-10 s
10-12 s
10-15 s
10 cm
10 mm
1 mm
10 nm
1 nm
0.1 nm
Ionic liquid
Structures of Diphenylacetylene in Different Electronic States
2099 cm-1
1567 cm-1
2223 cm-1
1974 cm-1
1500 1000 500
Wavenumber / cm-1
0min
11min
31min
41min
62min
72min
6min
24min
53min
69min
Time-resolved Raman Spectroscopy of a Dividing Yeast
Y-S Huang, T. Karashima, M. Yamamoto, H. Hamaguchi, J. Raman Spectrosc., 34, 1-3 (2003).
http://www.ed.kanazawa-u.ac.jp/~kashida/ChemII/chapter1/sec1/c112.htm
How Does Chemical Reaction Proceed?
When? Where?
Photophysics and Photochemistry of Molecules
S0
S1
S2
T1 Flu
ore
scen
ce
Ph
osp
horescen
c
Chemical
Reactions
Optical transition Vibrational relaxation Internal conversion Intersystem crossing
Ph
oto
excita
tion
Nanosecond Transient Raman Spectrometer (1983)
O OH
OH
H
3
O
*
2
HO OH
Benzophenonein the T1 state
(T1-BP)
h ISC
Benzopinacole
Benzophenone(BP)
Benzophenone ketyl radical
(BPK)
Benzhydrol(BH)
H-atom abstraction
Photochemical Hydrogen Abstraction Reaction of Benzophenone
T1
S1
S0
Probe: 532 nm
5 ns duration
15 ns delay
Pump: 266 nm
5 ns duration
Intersystem
crossing
Tn
Nanosecond Time-resolved Raman Spectroscopy of BP in CCl4
Pump + Probe
Probe only
T. Tahara, H. Hamaguchi and M. Tasumi, JPC (1987).
Fig.5
h1013C
d513C
h10
d10
d5
T1 Raman Spectra of Isotopically Substituted Benzophenones
O OH
OH
H
3
O
*
2
HO OH
Benzophenonein the T1 state
(T1-BP)
h ISC
Benzopinacole
Benzophenone(BP)
Benzophenone ketyl radical
(BPK)
Benzhydrol(BH)
H-atom abstraction
CO stretch
Raman Spectrum and Structure of T1 Benzophenone
1400 1800 1000 600
Raman Shift / cm-1
T1 state
S0 state
16
58
cm
-1
12
22
cm
-1
Photoisomerization of Trans-Stilbene
Probe solvent dependent structure and dynamics of S1 trans-stilbene by time-
resolved Raman spectroscopy
h Solvent-dependent isomerization rate
Hexane 70 ps
Dodecane 120 ps
Why, when and how rotation occurs in the excited state?
Nanosecond Transient Raman Spectrum
of S1 Trans-Stilbene (1983)
H. Hamaguchi, C. Kato, M. Tasumi, Chem. Phys. Lett., 100, 3-7 (1983).
Iwata, Yamaguchi, and Hamaguchi, Rev. Sci. Instrum. 64 , 2140 (1993).
cw Nd:YAG regenerative amplifier
cw mode-locked Nd:YAG laser
pulse compressor dye laser
SHG
optical delay
sample
multichannel detector (CCD)
pump
probe
SHG
polychromator
sync. pumped
band-reject filter
variable ND
UV cut filter
dichroic mirror
dichroic mirror
SHG
PD
82 MHz 588 nm
amplifier
dye AO
S0
Sn
S1 294 nm 2.2 ps
294 nm 2.2 ps
3.2 ps 588 nm
3.5 cm-1
3.2 ps 588 nm
3.5 cm-1
Trans-Stilbene
Picosecond Transform-limited Time-resolved Raman Spectrometer
Picosecond Transform-limited Time-resolved Raman
Spectroscopy
10
8
6
4
2
0
/
cm
-1
1086420
t / ps
Obs
(t = 3.2 ps, = 3.5 cm-1
)
Accurate peak position
and band shape
Picosecond Time-resolved Raman Spectra of S1 trans-Stilbene in CHCl3
1700 1600 1500 1400 1300 1200 1100
Raman Shift / cm-1
2 ps
20 ps
100 ps
-1 ps
0 ps
10 ps
7 ps
3 ps
30 ps
70 ps
-2 ps
50 ps
5 ps
1 ps
15 ps
40 ps
-10 ps Pump 294 nm
Probe 588 nm (0.1 mW)
C=C stretch vibration
1560 cm-1: double bond
Why rotation occurs
around a double bond ?
1620 1600 1580 1560 1540 1520
Raman Shift / cm-1
Hexane
Decane
Nonane
Octane
Heptane
Hexadecane
Dodecane
Fig. 7 H. Hamaguchi and K. Iwata
The C=C Stretch Raman Band of S1 trans-Stilbene in Alkanes
The peak position shifts to higher wavenumbers and the band width decreases
on going from hexane to hexadecane. Why?
1574
1572
1570
1568
Peak p
ositio
n /
cm
-1
22 21 20 19 18 17
Bandwidth / cm -1
hexane
octane
decane
Peak Position vs Band Width of the C=C Stretch Raman Band of S1 trans-
Stilbene In Alakne Solvents at Different Temperatures
Why does linear
Relation hold?
1578
1576
1574
1572
1570
1568
1566
Peak p
ositio
n /
cm
-1
20x10 9
15 10 5 0 k iso
/ s -1
283 K
293 K
298 K
303 K
313 K
Peak Position of the C=C Stretch Raman Band vs the
Isomerization Rate of S1 trans-Stilbene
Why does linear
relation hold ?
Why do lines
converge ?
気相
O N
C H
時間 /ps
双極子モーメント
/ D
Theory of Vibrational Dephasing and Band Shape
Simulation of Acetone/Acetonitrile system
Vibrational frequency is stochastically modulated in solution
Solvent-
induced
dynamic
polarization
Solvent-induced Dynamic Polarization of Acetone in
Acetonitrile
Formulation of Vibrational Band Shapes under Dynamic
Polarization
1
2
1
2
Modeling
-110 M: 2.94×
: 2.04 10-2
M×
: 1.35M: 2.29M
1. 0
0. 8
0. 6
0. 4
0. 2
0. 0
1000990980970960 1010
Raman shift / cm-1
inte
nsity
/arb
.unit
1 2
t =
(1-2)/W2
C=C
C+-C-
W 1
W 2
W 1
W 2
1 2
(c) Continuous Frequency Modulation Model
(b) Many Frequency Exchange Model
(a) Two Frequency Exchange Model
W = W1t/(1+t2)
G = W1t2/(1+t2)
G / W = t
),1/()/(2
1
2
11
tt +=W =
WWWn
),1/()/(22
1
2
11
tt +=G =
WWWn
+
=W0
02
1
)(
)1/()(
tt
tttt
dG
dGW
+
=G0
022
1
)(
)1/()(
tt
tttt
dG
dGW
G / W = t1/2 ; G(t)=exp(-ln2t2/t1/22)
Extension of the Two Frequency Exchange Model
Hamaguchi Mol. Phys.89, 463 (1997).
1574
1572
1570
1568
Peak p
ositio
n /
cm
-1
22 21 20 19 18 17
Bandwidth / cm -1
hexane
octane
decane
Peak Position vs Band Width of the C=C Stretch Raman Band of
S1 trans-Stilbene In Alakne Solvents at Different Temperatures
W = W1t/(1+t2)
G = W1t2/(1+t2)
G / W = t
t =1.4
1578
1576
1574
1572
1570
1568
1566
Peak p
ositio
n /
cm
-1
20x10 9
15 10 5 0 k iso
/ s -1
283 K
293 K
298 K
303 K
313 K
Peak Position of the C=C Stretch Raman Band vs the
Isomerization Rate of S1 trans-Stilbene
1=1577.3 cm-1
0
1
2
3
4
5
W
/ c
m-1
20x10 9
15 10 5 0 k iso
/ s -1
283 K
293 K
298 K
303 K
313 K
Peak Position of the C=C Stretch Raman Band vs the
Isomerization Rate of S1 trans-Stilbene
1x1012
W1
/ s-1
W = W1t/(1+t2)
t =1.4
W =0
0
1
2
3
4
5
W
/ c
m-1
20x10 9
15 10 5 0 k iso
/ s -1
283 K
293 K
298 K
303 K
313 K
Peak Position of the C=C Stretch Raman Band vs the
Isomerization Rate of S1 trans-Stilbene
1x1012
W1
/ s-1
kiso=
W1P(T)
1640 1600 1560 1520 1480
Raman shift / cm-1
Dodecane
Hexane Obs Fit
Fig. 10 H. Hamaguchi and K. Iwata
Fitting of the observed band shapes
Fitting of the C=C Stretch Raman Band of S1 trans-
Stilbene by the Two Frequency Exchange Model
W1=2.7x1012 sec-1 (370 (fs)-1)
W1=1.5x1012 sec-1 (670 (fs)-1)
W 1
W 2
W 1
W 2
W = W1t/(1+t2)
isomerization rate
Hexane 70 ps
Dodecane 120 ps
Isomeri-
zation
W1
W2
Dynamic Polarization Model of Isomerization
Hamaguchi, Iwata, CPL 208, 465 (1993).
Deckert, Iwata, Hamaguchi, J. Photochem. Photobiol. 102, 35 (1996).
Iwata, Ozawa, Hamaguchi, JCP 106, 3614 (2002).
kiso=W1P(T): Dynamic Polarization Model
E=3.5~3.7 kcal mol-1 (Raman band shape)
A new view on isomerization has come out of picosecond Raman spectroscopy !
kiso=Aexp(-E/RT) : Arrhenius formula
E=3.5 kcal mol-1 (fluorecsence lifetime)
kiso= W1P(T)
What Are Ionic Liquids? Liquids that are composed solely of ions
Why are they liquids? Green Solvents?
Liquid Structures?
Ionic Liquids
Crystal Liquid Crystal Liquid
Known condensed phases of matter
Are Ionic Liquids Really Liquids in the Conventional Sense?
Transparent but heterogeneous fluid
with well-defined local structures ?
Ionic Liquid ?
Picosecond Energy Dissipation Dynamics
of Photoexcited S1 Trans-stilbene
at 50 ps
Picosecond Raman Thermometer with S1 trans-
stilbene
K. Iwata and H. Hamaguchi, J. Phys. Chem. A, 101, 632 (1997)
Peak position
Temperature
Transient Raman spectra
S1 trans-stilbene at 50 ps
Raman
thermometer
pump 294 nm probe 588 nm C=C str.
High
temperature
Low
temperautre
37
Vibrational Cooling Process of
S1 Trans-stilbene in Decane
Peak shift to higher wavenumber
C=C str.
= 0.10 ps-1
pump 296 nm probe 592 nm
Time-resolved
Raman spectra
cooling
rate k
vibrational
cooling process
Cooling process
38
Correlation between
cooling rate and thermal diffusivity
K. Iwata and H. Hamaguchi, J. Phys. Chem. A, 101, 632 (1997).
Cooling rate
(Ultrafast dynamics)
Thermal diffusivity
(Bulk property)
Much faster cooling
rates in ionic liquids
Cooling Rate vs Thermal Diffusivity
Macroscopic and Microscopic Thermal Diffusion in
Ionic Liquids
Cooling rate
(microscopic)
Thermal diffusivity
(macroscopic)
between molecules
between
”Local Structures”
Absorption Spectrum of trans-stilbene in C2mimTf2N
2500 cm-1
① 325 nm excitation; No excess energy ② 297 nm excitation; Excess energy 2500 cm-1
②
①
Cooling Kinetics of S1trans-stilbene in C2mimTf2N
Coherent artifact
Simulation of Heat Dissipation in an Ionic Liquid
Tr.t. =T
2{ [erf{(a /2 + nL) (4Dtht)
1 2} +erf{(a /2 nL) (4Dtht)1 2}]
n =-
}
{ [erf{(b /2 + nL) (4Dtht)1 2} +erf{(b /2 nL) (4Dtht)
1 2}]n =-
}
{ [erf{(c /2 + nL) (4Dtht)1 2} +erf{(c /2 nL) (4Dtht)
1 2}]n =-
}
Temperature at the heat origin
a, b, c : Size of the
heat origin
L: Size of Local Structure
K. Iwata and H. Hamaguchi, J. Phys. Chem. A, 101, 632 (1997)
Heat origin:
Hot S1 trans-stilbene + solvent
Hot S1 trans-stilbene
Heat origin Local structure
Simulation of the Cooling Kinetics
Size of local structure > 10 nm
Photophysics ; closely lying excited states (S3, S2, S1, T1)
Photochemistry; photoisomerization
・Asymmeric trans-cis photoisomerization ・Marked solvent effect
Photobiology; retinoid proteins
・Rhodopsin ・Bcteriorhodopsin ・Sensoryrhodopsin
O 9-cis all-trans
Retinal: a prototype molecular system for
efficient
inefficient
O
Photoisomerization of All-trans Retinal
O
non-polar solvent
polar solvent Why?
O
O
O
O
O
13-cis
7-cis
11-cis
7 A ll-trans
9-cis
9 11 13 15
Proton Pumping by Bacteriorhodopsin
http://anx12.bio.uci.edu
All-trans isomerizes to 13-cis exclusively. Why and How?
9-cis All-trans
S3
S2
S1
S0
T1
O
O
What happens in the Excited electronic
States of Retinal ?
h h
Nanosecond Pump/Probe Time-resolved Raman
Spectroscopy of Retinal Isomers
H. Hamaguchi, H. Okamoto,and M. Tasumi, Chem. Lett. 1984, 549-550.
H. Hamaguchi, H. Okamoto, M. Tasumi, Y. Mukai, and Y. Koyama,
Chem. Phys. Lett. 107, 355-359 (1984).
Tn
T1
S1
S0
Probe: 532 nm
5 ns duration
15 ns delay
Pump: 355 nm
5 ns duration
Intersystem
crossing
Raman
Scattering
Raman Spectra of All-trans- and 9-cis-Retinal in the T1 and S0 States
All-trans-retinal
T1 State S0 State
9-cis-retinal
T1 State S0 State
9-cis All-trans
S3
S2
S1
S0
T1
O
O
15 ns after
excitation
One-way Photoisomerization on the T1 surface
h h
10 Picosecond Time-frequency Two-dimensional
Multiplex CARS Spectroscopy of Retinal Isomers
Tn
T1
S1
S0
Pump: 400 nm
500 fs duration
Intersystem
crossing
T. Tahara, B. N. Toleutaev, and H. Hamaguchi, J. Chem. Phys. 217, 369-374 (1994).
T. Tahara and H. Hamaguchi, Rev. Sci. Instru. 65, 3332-3338 (1994).
1 2
1
21-2
Probe:
1 523 nm, 5 ns
2 broadband, 5ns
Experimental Setup for 2-D CARS Spectroscopy
Wavenumber range: ~600 cm-1
Time-resolution: 15 ps
Picosecond Two-dimensional Multiplex CARS Spectroscopy
(2-D CARS)
http://cvitae.org/content/view/180/895/
Operation Principle of a Streak Camera
2-D CARS Image for All-trans-retinal in
Cyclohexane
Wavenumber / cm-1 Wavenumber / cm-1
Picosecond Time-resolved CARS Spectra of Retinal Isomers
in Cyclohexane
All-trans 9-cis
Population Rise of the All-trans T1 State Monitored by CARS
890 ps
9-cis All-trans
S3
S2
S1
S0
T1
O
O
Photoisomerization on the Triplet Potential Surface
900 ps
Asymmetric: cis
to trans only h h
Nanosecond Pump/Probe Time-resolved Infrared
Absorption Spectroscopy of Retinal Isomers
Tn
T1
S1
S0
Pump: 347 nm
5 ns duration
Intersystem
crossing
T. Yuzawa and H. Hamaguchi, J. Mol. Struct., 352, 489-495.
T. Yuzawa and H. Hamaguchi, in preparation.
Probe:
cw infrared continuum
Nanosecond Time-resolved Infrared Absorption Spectrometer
4000 cm-1 ~ 700 cm-1
50 ns time resolution
Time-resolved Infrared Absorption Spectra of Photoexcited
All-trans-retinal in Cyclohexane
Singular Value Decomposition (SVD) Analysis
SVD Analysis of the Time-resolved Infrared Absorption Spectra of All-trans Retinal
Spectral component Singular Values Temporal component
SVD Analysis of the Time-resolved Infrared Absorption Spectra
of All-trans Retinal
1.0
0.5
0.0
Am
plit
ud
e
403020100
Time / ms
1.0
0.5
0.0
Am
plit
ud
e
403020100
Time / ms
all-trans S0
h
all-trans S1
all-trans T1
13-cis S0 9-cis S0
ISO = 0.27 ~0.43
3 : 1
ISC = 0.43~0.7
QY_estimation4
The schematic diagram of the photoisomerization mechanism of all- trans-retinal
ISO =
[photoexcited all-trans S0]
[13-cis S0 + 9-cis S0]
(calculated)
(literature)
photoisomerization via the singlet excited state
Conclusion 1
Photoisomerization Pathway of All-trans-retinal in
Cyclohexane
9-cis All-trans
S3
S2
S1
S0
T1
O
O
5 ms << 50 ns
Two Relaxation Pathway of the Photoexcited All-trans-retinal
h
Femtosecond Pump/Probe Time-resolved Visible and
Ultraviolet Absorption Spectroscopy of Retinal Isomers
Tn
T1
S1
S0
Intersystem
crossing
S. Yamaguchi and H. Hamaguchi, J. Mol. Struct. 379, 87-92 (1996).
S. Yamaguchi and H. Hamaguchi, J. Chem. Phys. 109, 1397-1408 (1998).
H. Minami and H. Hamaguchi, to be published.
S2
S3
Probe:
Femtosecond
White Cntinuum
Pump:
400 nm
50 fs duration
Femtosecond Time-resolved Visible/Ultraviolet Absorption System
Chirp Correction for the Observed Femtosecond Time-
resolved Absorption Spectra
Femtosecond Time-resolved Visible Absorption Spectra in Hexane
All-trans 9-cis
Wavelength / nm Wavelength / nm
Cascading Decay Kinetics of Photoexcited All-trans-retinal in
Heptane
Excitation: 400 nm
9-cis All-trans
S3
S2
S1
S0
T1
O
O
50 fs
400 fs
32 ps
34 ps
700 fs
50 fs
Femtosecond Photoexcitation Dynamics of Retinal Isomers
h h 5 ms
900 ps
Femtosecond Time-resolved Ultraviolet Absorption
Spectra of All-trans retinal in Hexane
Wavelength / nm
SVD Analysis of the Femtosecond Time-resolved Ultraviolet
Absorption Spectra of All-trans-retinal in Hexane
9-cis All-trans
S3
S2
S1
S0
T1
O
O
7 ps
Trans to Cis Isomerization via the S2 state
9-cis All-trans
S3
S2
S1
S0
T1
O
O
50 fs
400 fs
32 ps
34 ps
700 fs
50 fs
Photoisomerization Pathways and Dynamics of Retinal Isomers
h h 5 ms
900 ps 7 ps
Picosecond Time-resolved 2-D CARS Spectroscopy with an
Optical Kerr Gating
Streak camera
Ti:sapphire
oscillator / regenerative
amplifier system SHG
Optical delay
Spectro-
graph ns Nd:YLF
& dye laser
Sample Kerr cell
Analyzer Filter
Filter
waveplate Gating pulse
~800 nm
Polarizer
Excitation
pulse
~400 nm
Actinic light: 90°
1: 90°
2: 90°
Analyzer: 0°
Detector
Gate pulse: 45º
CARS signal: 90º
Kerr medium (CS2)
Optical Kerr Gating
Optical Kerr Gated Picosecond CARS
Spectroscopy
Picosecond Time-resolved CARS Spectra of
Photoexcited All-trans Retinal in Ethanol : Simulation
K. Ishii and H. Hamaguchi, Chem. Phys. Lett, 367, 672 (2003).
First Observation of the key intermediate S2
S0
S2
S0+T1
S3
trans
h
S0
T1
S1 S2
P*
P0
S0
cis
“perpendicular”
Large band width of the C=C band (100 cm-1)
Very fast vibrational dephasing
Dynamic polarization model of isomerization
0
・S2の振動スペクトル測定に初めて成功
・C=C伸縮バンドの顕著な広幅化(100cm-1)
異性化反応の動的分極理論と符合
S0
T1
S1
S3
S2
P*
P0
S0
trans cis
“perpendicular”
h
S0の減少
S2の生成、消滅
S0の回復
Cis体の生成
T1の生成
動的分極
9-cis All-trans
S3
S2
S1
S0
T1
O
O
Ns Raman
10ps CARS
Ns IR
Fs UV-VIS Ps CARS
Time-resolved Spectroscopies Look at Photoisomerization of
Retinal
Isomeri-
zation
W1
W2
Dynamic Polarization Model of Isomerization
Hamaguchi, Iwata, CPL 208, 465 (1993).
Deckert, Iwata, Hamaguchi, J. Photochem. Photobiol. 102, 35 (1996).
Iwata, Ozawa, Hamaguchi, JCP 106, 3614 (2002).
kiso=W1P(T): Dynamic Polarization Model
E=3.5~3.7 kcal mol-1 (Raman band shape)
A new view on isomerization has come out of picosecond Raman spectroscopy !
kiso=Aexp(-
E/RT) : Arrhenius formula
E=3.5 kcal mol-1 (fluorecsence lifetime)
kiso= W1P(T)
9
O 7 9 11
O
13 1 5
7 11 13
O
1 5
7 9 11 13 1 5
hyperconjugation
014
Dynamic Polarization Model for the Retinal
Photoisomerization
Why are 13-cis and 9-cis selected?
hyperconjugation
Absolute Temperature Determination
with Stokes/anti-Stokes Raman spectroscopy
Temperature
at the laser focal spot?
Stokes/anti-Stokes Raman Scattering
|v=0>
|v=1>
Stokes antiStokes
Boltzmann factor
Off-resonance Raman scattering
Sensitivity Calibration with Standard Light
Rotational Raman spectra as primary intensity standard
[1] H. Hamaguchi, I. Harada, T. Shimanouchi, Chem. Lett. 1974, 12, 1405-1410.
Previous study [1]
Sensitivity calibration with D2
D2[1]
Accuracy of the
Standard Intensity
Accuracy of
Sensitivity Calibration
This study
Sensitivity calibration with N2
-200 ~ +200 cm-1, 40 lines
Suitable for low-frequency region
1.0
0.8
0.6
0.4
0.2
0.0
cross
-sec
tion r
atio
2015105
Initial J
Calculated Raman Cross Section Ratios of N2
Intensity Standard
cross-section
Low Frequency Raman Microspectrometer
Spectral resolution: 1 cm-1
Nd:YVO4
Laser (532 nm)
Sample
Polarizer
Brag Notch filters
Spectrometer
f=50 cm
1800 gr/mm
Beam
sampler
Objective (x20
NA0.45)
Pinhole
(75 um)
CCD
Long pass
filter
Halogen lamp
Raman
scattering
Optical
image
Dichroic
mirror
Rotational Raman Spectrum of N2
532 nm, 20 mW, x 20 Objective,
exposure: 30 min, resolution: 1.3 cm-1
Background (glass, air) was subtracted
0
Inte
nsi
ty /
a.u
.
200 100 0 -100 -200
Raman shift / cm-1
Trace Naphthalene Melting
Spectral resolution: 1 cm-1
Peltier
heat/cool stage
Thermocouple
(on the stage)
Sample
Naphthalene
Mp. 353 K (80 °C)
532 nm, 4 mW, x 20 Objective
Exposure: 0.1 sec
Cycle: 0.22 sec / spectrum
Heat speed: 20 K / min
(on the heat stage)
Low-frequency Raman Spectrum of Naphthalene
532 nm, 4 mW, x 20 Objective,
exposure: 80 sec
Temperature determination
(-30 to -170 cm-1)
solid
400 200 0 -200Raman shift / cm -1
(b)
174.6 s
191.4 s
192.7 s
100 μm
420
400
380
360
340
320
300
280
Tem
per
atu
re /
K
200150100500Heat time / sec
m.p.
Heating
(a)
Solid
Liquid
2)
plateau
(50~120
s)
3)
fluctuation
(120 ~ 192 s)
> 50
K
4) melting
(192.7 s~)
Unusual Thermal Behavior before Melting
0) at r.t.
(< 0 s)
1)
increasing
to m.p.
(0~50 s) Local temperature fluctuation just before melting?