Elementary Processes and Thermodynamic Properties of ...
Transcript of Elementary Processes and Thermodynamic Properties of ...
3rd CRP β I.A.E.A., Vienna 2016
ROBERTO CELIBERTO
Dipartimento di Ingegneria Civile, Ambientale, Edile, del Territorio e di Chimica
Politecnico di Bari (Italy)
and
Istituto di Nanotecnologia - CNR, Bari (Italy)
Elementary Processes and Thermodynamic
Properties of Hydrogen and Helium Plasmas
High-density hydrogen plasma
Debye plasma: π½(π) =ππ
πβ πβπ/ππ« (πD = Debye radius)
Non-ideal effects
β’ Self-energy (surrounding plasma influence):
π¬ =ππ
ππ- self-energy term =
ππ
ππ-
ππ
πππ«
β’ Alteration of the bound states energy:
HY = E Y π =πππ
πππ-ππ
πβ πβπ/ππ« -
ππ
πππ«
- Finite number of bound states- Lowering of bound states- Lowering of the ionization potential (Mott effect)
High-density hydrogen plasma
Debye plasma: π½(π) =ππ
πβ πβπ/ππ« (πD = Debye radius)
Non-ideal effects
πβ + π+ β π―
β’ Ionization degree from Saha equation (including self-energy and bound states)
β’ Lowering of the ionization potential at high densitiescauses full ionization (pressure ionization)
EXCITED-STATE KINETICS AND RADIATION TRANSPORT IN LOW-TEMPERATURE PLASMAS
THE SELF-CONSISTENT MODEL
G Colonna, G DβAmmando, LD Pietanza, M Capitelli,Plasma Physics & Controlled Fusion, 57, 014009 (2015)
Hydrogen and helium
1s2
EXCITED-STATE KINETICS AND RADIATION TRANSPORT IN LOW-TEMPERATURE PLASMAS
THE SELF-CONSISTENT MODEL
G Colonna, G DβAmmando, LD Pietanza, M Capitelli,Plasma Physics & Controlled Fusion, 57, 014009 (2015)
EXCITED-STATE KINETICS AND RADIATION TRANSPORT IN LOW-TEMPERATURE PLASMAS
SHOCK TUBE RESULTS: TEMPERATURES
G Colonna, G DβAmmando, LD Pietanza, M Capitelli,Plasma Physics & Controlled Fusion, 57, 014009 (2015)
EXCITED-STATE KINETICS AND RADIATION TRANSPORT IN LOW-TEMPERATURE PLASMAS
SHOCK TUBE RESULTS: LEVEL DISTRIBUTION AND EEDF
Ionization limit
n = 2 n = 2
Ionization limit
G Colonna, G DβAmmando, LD Pietanza, M Capitelli,Plasma Physics & Controlled Fusion, 57, 014009 (2015)
π+ πππ+ βΆππ+ ππ+
Quasi-Classical Trajectory (QCT) method
Quantum-Mechanical Close-Coupling (QM-CC) method
QCT ββ F. Esposito, C.M. Coppola, D. De Fazio J. Phys. Chem. A, 119, 12615 (2015).QM-CC ββ D. De Fazio, Phys. Chem. Chem. Phys., 16, 11662 (2014)
Exit channel
Ramachandran et al, Chem. Phys. Lett., 469, 26 (2009)
Entrance channel
Hβ¦H distance (a.u.)Heβ¦H distance (a.u.)
En
erg
y (
eV
)
H-H = 2.074 (a.u.)
He-H = 1.927 (a.u.)
He+H2+
HeH++H
MRCI (cc-pv5z)
Fitted at (M = 6)
Calculated
MRCI (cc-pv5z)
Fitted at (M = 6)
Calculated
π+ πππ+ βΆππ+ ππ+
(Gamallo et al,J Phys. Chem., 2104)
(Bovino et al, Astron. Astrophys., 2011)
QM-CC
QM-WP
QM-CS/NIP
QCT
π+ πππ+ βΆππ+ ππ+
QCT ββ F. Esposito, C.M. Coppola, D. De Fazio J. Phys. Chem. A, 119, 12615 (2015).QM-CC ββ D. De Fazio, Phys. Chem. Chem. Phys., 16, 11662 (2014)
(Rutherford & Vroom, J. Chem. Phys, 1973)Exp.
QM-CC
QCT
π+ πππ+ βΆππ+ ππ+
QCT ββ F. Esposito, C.M. Coppola, D. De Fazio J. Phys. Chem. A, 119, 12615 (2015).QM-CC ββ D. De Fazio, Phys. Chem. Chem. Phys., 16, 11662 (2014)
v = 0
QM-CC
Solid lines
QCT
Dashed lines
π+ πππ+ βΆππ+ ππ+
QCT ββ F. Esposito, C.M. Coppola, D. De Fazio J. Phys. Chem. A, 119, 12615 (2015).QM-CC ββ D. De Fazio, Phys. Chem. Chem. Phys., 16, 11662 (2014)
j = 0
v = 0v = 2
v = 4
Exp.: Rutherford & Vroom,J. Chem. Phys, 1973)
QCT results
π+ πππ+ βΆππ+ ππ+
QCT ββ F. Esposito, C.M. Coppola, D. De Fazio J. Phys. Chem. A, 119, 12615 (2015).QM-CC ββ D. De Fazio, Phys. Chem. Chem. Phys., 16, 11662 (2014)
QM-CC
Solid lines
QCT
Dashed lines
π+ πππ+ βΆππ+ ππ+
QCT ββ F. Esposito, C.M. Coppola, D. De Fazio J. Phys. Chem. A, 119, 12615 (2015).QM-CC ββ D. De Fazio, Phys. Chem. Chem. Phys., 16, 11662 (2014)
Billingβs semiclassical method:
β’ Classical description of the gas-phase atoms (trajectories)
β’ Quantum mechanical description of surface
β’ Recombination coefficient (gH) and probability are calculated
Unit cell for
W(110) plane
Cristal used in
the calculations
M. Rutigliano, D. Santoro and M. Balat-Pichelin, Surface Science, 628, 66 (2014)
Hydrogen recombination on tungsten at high temperature: experiment and molecular dynamics simulation
a
H-atom interaction
potentials
a
M. Rutigliano, D. Santoro and M. Balat-Pichelin, Surface Science, 628, 66 (2014)
H2-molecule interaction potential for T site
a
eV eV
H2-molecule interaction potential for T site
H
r
H
zH
xH
yH
a
eV eV
Hπππ β W 110 + Hπππ βΆ H2πππ +W(110)
Hπππ β W 110 + Hπππ βΆHπππ β W 110 + Hπππ
Hπππ β W 110 + Hπππ βΆHπππ β W 110 + Hπππ
Hπππ β W 110 + Hπππ βΆ Hπππ β W 110 +Hπππ β W 110
Hπππ β W 110 + Hπππ βΆHπππ +Hπππ +W 110
Hπππ β W 110 + Hπππ βΆ (H2)πππ β W 110
Molecular
recomb.
Ads/des
Exchange
Atomic
Ads
Molecular
ads
Des
Surface processes
The calculations have been performed for the 3F and T sites
Recom
bin
ation p
robabili
ty
Hπππ β W 110 + Hπππ βΆ H2πππ +W(110)
T = 1000 K
M. Rutigliano, D. Santoro and M. Balat-Pichelin, Surface Science, 628, 66 (2014)
M. Rutigliano, D. Santoro and M. Balat-Pichelin, Surface Science, 628, 66 (2014)
On the surface Above the surface
H atom trajectories
M. Rutigliano, D. Santoro and M. Balat-Pichelin, Surface Science, 628, 66 (2014)
πΎπ» =[Hrec]
[Htot]
M. Rutigliano, D. Santoro and M. Balat-Pichelin, Surface Science, 628, 66 (2014)
π¦ = 1.98 β exp(β1693/π)
TS = Tgas
πΎπ» =[Hrec]
[Htot]
M. Rutigliano, D. Santoro and M. Balat-Pichelin, Surface Science, 628, 66 (2014)
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
πππ+ πΏππΊπ
+, π + π βΆ πππ+ π¨ππΊπ
+ + πβΆ ππ + ππ+ + π
R. Celiberto, K. Baluja, R. K. Janev and V. Laporta,Plasma Phys. Control. Fusion 58, 014024 (2015)
πππ+ πΏππΊπ
+, π + π βΆ πππβ βΆππ +ππ+ + π
πππ+ πΏππΊπ
+, π + π βΆ πππβ βΆπππ
+ πβ² + π
J. Royal and A. E. Orel 75, 052706 (2007)
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
πππ+ πΏππΊπ
+, π + π βΆ πππ+ π¨ππΊπ
+ + πβΆ ππ + ππ+ + π
R. Celiberto, K. Baluja, R. K. Janev and V. Laporta,Plasma Phys. Control. Fusion 58, 014024 (2015)
πππ+ πΏππΊπ
+, π + π βΆ πππβ βΆππ +ππ+ + π
πππ+ πΏππΊπ
+, π + π βΆ πππβ βΆπππ
+ πβ² + π
J. Royal and A. E. Orel 75, 052706 (2007)
π¨ππΊπ+
πΏππΊπ+
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
πππ+ πΏππΊπ
+, π + π βΆ πππ+ π¨ππΊπ
+ + πβΆ ππ + ππ+ + π
R. Celiberto, K. Baluja, R. K. Janev and V. Laporta,Plasma Phys. Control. Fusion 58, 014024 (2015)
Adiabatic Nuclei Approximation
π¨ππΊπ+
πΏππΊπ+
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
πππ+ πΏππΊπ
+, π + π βΆ πππ+ π¨ππΊπ
+ + πβΆ ππ + ππ+ + π
R. Celiberto, K. Baluja, R. K. Janev and V. Laporta,Plasma Phys. Control. Fusion 58, 014024 (2015)
Adiabatic Nuclei Approximation
π¨ππΊπ+
πΏππΊπ+
Outer Region
Single-center expansionβ¦
Boundary of R-matrix box
Inner Region
Exchange,
Short-range correlationβ¦
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
R-matrix method
πππ+ πΏππΊπ
+ + π βΆ πππ+ π¨ππΊπ
+ + π βΆ ππ + ππ+ + π
e-
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
A2Ξ£π+
X2Ξ£π’+
Xie J, Poirier B and Gellene G I
J. Chem. Phys. 122 184310 (2005)
R-matrix
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
Metropoulos A, Li Y, Hirsch G and Buenker R J
Chem. Phys. Lett. 198 266 (1992)
R-matrix
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
v = 0
Adiabatic
nuclei approx
Fixed-nuclei
Approx.
(Req = 2.04 a.u.)
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion
v = 0
v = 0
Electron-impact dissociation cross sections of vibrationally excited He2
+ molecular ion0
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3rd CRP β I.A.E.A., Vienna 2016
ROBERTO CELIBERTO
Dipartimento di Ingegneria Civile, Ambientale, Edile, del Territorio e di Chimica
Politecnico di Bari (Italy)
and
Istituto di Nanotecnologia - CNR, Bari (Italy)
Elementary Processes and Thermodynamic
Properties of Hydrogen and Helium Plasmas