teorijska analiza ultrabrzih procesa · ic spektri i asignacija traka (3) f. gatti and h-d. meyer,...
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![Page 1: TEORIJSKA ANALIZA ULTRABRZIH PROCESA · IC SPEKTRI I ASIGNACIJA TRAKA (3) F. Gatti and H-D. Meyer, Chem. Phys. 301 (2004) 3 IVR –intramolecular vibrational energy redistribution](https://reader030.vdocuments.site/reader030/viewer/2022040800/5e379813f265cf429b1b00dc/html5/thumbnails/1.jpg)
TEORIJSKA ANALIZA ULTRABRZIH PROCESA
NOVE FIZIČKOHEMIJSKE METODE
MILENA PETKOVIĆ
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ultrabrzi procesi
vremenski nezavisna Šredingerova jednačina
vremenski zavisna Šredingerova jednačina
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• hemijske reakcije inicirane sudarom čestica ili povišenjem temperature
• interakcija čestica sa elektromagnetnim zračenjem: fotofizika i fotohemija
ULTRABRZI PROCESI
Ultrabrzim procesima nazivamo procese koji se odvijajuu opsegu od nekoliko atosekundi (10-18s) do nekoliko nanosekundi (10-9s).
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vremenski zavisna Šredingerova jednačina
ttH
t
ti
ˆ
vremenski nezavisna Šredingerova jednačina
EH
OSNOVNI ALAT TEORETIČARA
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vreme života prelaznog stanja ≈ 10 - 100 fs
reakciona koordinata
reaktanti
proizvodi
prelazno stanje
PRELAZNO STANJE
Ea
E
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ultrabrzi procesi
vremenski nezavisna Šredingerova jednačina
vremenski zavisna Šredingerova jednačina
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PROMENE DUŽ PUTA MINIMALNE ENERGIJE
E. G. Lewars, The concept of the Potential Energy Surface in Computational Chemistry (Springer, Cham, 2016)
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PROMENE DUŽ PUTA MIN. ENERGIJE (1)
Đ. Nakarada, M. Petković, Int. J. Quantum Chem. 118 (2017) e25496
C6H4(OH)2 + OH• = C6H3(OH)2• + H2O
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PROMENE DUŽ PUTA MIN. ENERGIJE (2)
Đ. Nakarada, M. Petković, Int. J. Quantum Chem. 118 (2017) e25496
C6H4(OH)2 + OH• = C6H3(OH)2• + H2O
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RAZLIČITI REAKCIONI PUTEVI (1)
M. Petković, Đ. Nakarada, M. Etinski, J. Comp. Chem. 39 (2018) 1868
C6H4(OH)2 + CH3O• = C6H3(OH)2• + CH3OH
Ea = 23 kJ/mol Ea = 25 kJ/mol
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RAZLIČITI REAKCIONI PUTEVI (2)
M. Petković, Đ. Nakarada, M. Etinski, J. Comp. Chem. 39 (2018) 1868
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NASTANAK I KIDANJE HEM. VEZE (1)
B. Milovanović, M. Etinski, M. Petković, J. Serb. Chem. Soc. (2019) in press
C6H4(OH)2 + CH3O• = C6H3(OH)2• + CH3OH
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NASTANAK I KIDANJE HEM. VEZE (2)
B. Milovanović, M. Etinski, M. Petković, J. Serb. Chem. Soc. (2019) in press
fragmenti reaktanti:C6H4(OH)2 + CH3O•
fragmenti proizvodi:C6H3(OH)2• + CH3OH
informacije o vezi koja nastaje
informacije o vezi koja se kida
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ultrabrzi procesi
vremenski nezavisna Šredingerova jednačina
vremenski zavisna Šredingerova jednačina
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ANALIZA DINAMIKE SISTEMA
G. Stock, W. Domcke, Conical Intersections in Femtosecond time-resolved spectroscopy of the dynamics at conical intersections (World Scientific Singapore, 2003)
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M. Petković, Chem. Phys. 331 (2007) 438
stepen
slobode harm. anh. eksp.a
1 1800 1766 1737
2 1342 1314 1293
3 828 820 809
4 786 777 780
5 731 719 711
6 561 561 563
7 436 431 434
8 250 254 273
9 135 158 122
1
2346
7
?
?
?
prelaz izr. eksp.b
? 1434 1424
? 1118 1119
? 993 988
frekvencija / cm-1
frekvencija / cm-1
dx
dy
a Orphal et al. J. Phys. Chem. A 101 (1997) 1062
b Miller et al. Spec. Acta 23A (1967) 223
IC SPEKTRI I ASIGNACIJA TRAKA (1)
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= 1434 cm-1
= 1118 cm-1
= 993 cm-1
E5
E2E1,3,4,6-9
E6
E2E3
E4 E1,5,7-9
E6
E7
E3E2
E4
E1,5,8,9
IC SPEKTRI I ASIGNACIJA TRAKA (2)
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frekvencija / cm-1
stepen
slobode harm. anh. eksp.a
1 1800 1766 1737
2 1342 1314 1293
3 828 820 809
4 786 777 780
5 731 719 711
6 561 561 563
7 436 431 434
8 250 254 273
9 135 158 122
1
2346
725
26
6+ 7
prelaz izr. eksp.b
25 1434 1424
26 1118 1119
6+ 7 993 988
frekvencija / cm-1dx
dy
M. Petković, Chem. Phys. 331 (2007) 438
a Orphal et al. J. Phys. Chem. A 101 (1997) 1062
b Miller et al. Spec. Acta 23A (1967) 223
IC SPEKTRI I ASIGNACIJA TRAKA (3)
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F. Gatti and H-D. Meyer, Chem. Phys. 301 (2004) 3
IVR – intramolecular vibrational energy redistribution
vCH = 5vCH = 1
INTRAMOLEKULSKA PRERASPODELAVIBRACIONE ENERGIJE
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M. Petković and O. Kühn, Chem. Phys. 301 (2004) 91
KONTROLA HEMIJSKE REAKCIJE IINTRAMOLEKULSKA PRERASPODELA
VIBRACIONE ENERGIJE
H D
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http://www. biofysisk.kemi.dtu.dk/Research/Physical/crd.aspx
KONTROLA HEMIJSKE REAKCIJE
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HOD*
H+OD
HO+D
N. Elghobashi, P. Krause, J. Manz and M. Oppel, PCCP, 5 (2003) 4806
)(
)0,()0,(
1
00
SHOD
vSHODvSHOD
UV
IR
ODH
DHO
HOD
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HOD*
H+OD
HO+D
N. Elghobashi, P. Krause, J. Manz and M. Oppel, PCCP, 5 (2003) 4806
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J. Michl and V. Bonačić-Koutecky, Electronic aspects of organic Photochemistry, John Wiley & Sons: New York, 1990
KONTROLA HEMIJSKE REAKCIJE
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ultrabrzi procesi (atosekundna – nanosekundna skala)
vremenski nezavisna Šredingerova jednačina(analiza svojstava sistema duž puta minimalne energije,asignacija spektralnih traka)
vremenski zavisna Šredingerova jednačina(vremenska evolucija sistema, kontrola hemijske reakcije)
REZIME