CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
M. CAPITELLI
CNR IMIP BARI – ITALY
DEPT OF CHEMISTRY, UNIVERSITY OF BARI – ITALY
ELEMENTARY PROCESSES, THERMODYNAMICS AND TRANSPORT OF
H2, O2 AND N2 PLASMAS
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
C.GORSE, S.LONGO, P.D IOMEDE, C.CATALFAM O, G.D’AMMANDO, M.C.COPPOLA Department of Chemistry, University of Bari, Bari , Italy
D.BRUNO, G.COLONNA, O.DE PASCALE, F.ESPOSITO, A.LARICCHIUTA
M.CACCIATOR E, M.RUTIGLIANO
IMIP(CNR), Bari, Bari, Italy
R.CELIBERT O
Department of Water Engineering an d Chemistry Polytechnic of Bari, Bari, Italy
COLLABORATORs
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
a) photodissociation of H2(), D2(), HD() and H2+()
b) heavy particle collision cross sections : H2(), D2() from recombinationc) H2() formation on graphited) heavy particle collision cross sections for O-O2 and N-N2 : fitting relationsd) collision integrals for O-O and O-O+ interactionse) collision integrals for N-N and N-N+ interactions: a phenomenological
approach
a) thermodynamic properties of atomic hydrogen plasmab) transport properties of atomic hydrogen plasma: cut-off criteriac) negative ion source modeling
ELEMENTARY PROCESSES
OUTLINE
THERMODYNAMICS, TRANSPORT AND KINETICS OF PLASMAS
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
PHOTODISSOCIATION PROCESSES for H2(), D2(), HD() and H2+()
• LYMAN and WERNER SYSTEMS• HIGH-ENERGY EXTRAPOLATION for STATE-DEPENDENT CROSS SECTIONS• derivation of
• STATE-DEPENDENT PHOTODISSOCIATION RATE COEFFICIENTS• MACROSCOPIC PHOTODISSOCIATION RATE COEFFICIENT (ktot) • FITTING FORMULAS
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
D.R.G. Schleicher et al. Astronomy&Astrophysics 490 (2008) 521
10-5
10-3
10-1
101
103
105
107
103 104
TEMPERATURE [K]
i=0
ktot
10-5
10-3
10-1
101
103
105
107
103 104
TEMPERATURE [K]
i=0
ktot
10-5
10-3
10-1
101
103
105
107
103 104
TEMPERATURE [K]
i=0
ktot
MACROSCOPIC PHOTODISSOCIATION RATE COEFFICINTS for H2() and H2
+() : COMPARISON with LITERATURE
H2() LYMAN H2() WERNER
H2+()
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
HEAVY PARTICLE COLLISIONSVIBRATIONALLY EXCITED MOLECULES FROM RECOMBINATION
• QCT SIMULATION
• RECOMBINATION RATE COEFFICIENTs
• from QCT DISSOCIATION by DETAILED BALANCE THREE-BODY RECOMBINATION
• from RBC (Roberts, Bernstein & Curtiss) THEORY TWO-STEP BINARY COLLISION
Potential Energy
Internuclear Distance
rotational barrier
quasi-bound state
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
T = 1,000 K T = 300 K
10-35
10-34
10-33
10-32
0 2 4 6 8 10 12 14
VIBRATIONAL QUANTUM NUMBER
detailed balance
RBC theory
10-36
10-35
10-34
10-33
10-32
10-31
10-30
0 2 4 6 8 10 12 14
VIBRATIONAL QUANTUM NUMBER
detailed balance
RBC theory
H2() FROM RECOMBINATION
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
O2(), N2() FROM RECOMBINATION
O2 N2
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
ATOMIC RECOMBINATION on GRAPHITE SURFACEH2 (, j) NASCENT DISTRIBUTIONs
• SEMI-CLASSICAL MODEL• ELEY-RIDEAL MECHANISM (H CHEMISORBED at the SURFACE with a chemisorption well of 0.52eV )• PROBABILITIES dependence on
• SURFACE TEMPERATURE• IMPACT ENERGY• ISOTOPES
SURFACE TEMPERATURE=500 K ENERGY = 0.07 eV
M.RUTIGLIANO, M.CACCIATORE, CHEM.PHYS.CHEM. 9 (2008) 171
vibrational distribution is obtained summing up population
of rotational levels
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
HEAVY PARTICLE COLLISION CROSS SECTIONS for O-O2 and N-N2 SYSTEMSFITTING RELATIONS
• ACCURATE QCT CROSS SECTIONS for• VIBRATIONAL DEACTIVATION VT processes• DISSOCIATION
F.ESPOSITO, I.ARMENISE, G.CAPITTA, M.CAPITELLI, CHEM.PHYS 351 (2008) 91
fitting bidimensional
relations
EASY INCLUSION in KINETIC MODEL
TEMPERATURE
RA
TE
CO
EF
FIC
IEN
T [
cm3 s
-1]
TEMPERATURE
RA
TE
CO
EF
FIC
IEN
T [
cm3 s
-1]
i=30
i=40
i=46
i=010
20
30
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
COLLISION INTEGRALS for O-O and O-O+ INTERACTIONS involving LOW-LYING EXCITED STATES
SCHEME OF CLASSICAL APPROACH
ab-initio INTERACTION POTENTIALSfor molecular (atom-atom)
or molecular ion (atom-ion) states
exchange cross sectionsQex
DEVOTO formula
splitting gerade-ungerade
orasymptoticapproach
ELASTIC COLLISIONS
Morse interpolation(bound states)
exponential interpolation(repulsive states)
Smith&Munntabulated collision integrals
Kalinin&Dubrovitskiiformulas
Ω(1,1)( )nΩ(2,2)
( )n
averaging procedure
Ω(2,2)
[(Ω(1,1))2 + (Ω(1,1))2]1/2el ex
INELASTIC COLLISIONS excitation or charge exchange
Ω(1,1)
= 1/2[ - ( )]Q C D ln g2ex
Ω( , )s= € l Σ w Ω( ,s)(n) (n) € lΣ w(n)
viscosity-typecollision integrals
diffusion-typecollision integrals
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
A.LARICCHIUTA, D.BRUNO, M.CAPITELLI, R.CELIBERTO, C.GORSE, G.PINTUS, CHEM.PHYS.LETT. 344 (2008) 13
EFFECTIVE DIFFUSION-TYPE COLLISION INTEGRALSfor O-O+ INTERACTIONS involving LOW-LYING EXCITED STATES
ELASTIC CONTRIBUTION from POTENTIALS andINELASTIC CONTRIBUTION from CHARGE-EXCHANGE CROSS-SECTIONS
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
A PHENOMENOLOGICAL MODEL forHEAVY PARTICLE COLLISION INTEGRALS
CLASSICAL COLLISION INTEGRALS
INTERACTION POTENTIAL
PHENOMENOLOGICAL APPROACHAVERAGE INTERACTION
fitting formulas up to (4,4) orderA. LARICCHIUTA, G.COLONNA et al. Chemical Physics Letters 445 (2007) 133
“tuplet” ( ) characterising the colliding system
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
PHENOMENOLOGICAL APPROACH
ION-NEUTRAL4
6
INTERACTION POTENTIAL FEATURES
correlation formulas from physical properties of colliding partnersPOLARIZABILITY, CHARGE and
NUMBER of ELECTRONS EFFECTIVE in POLARIZATION
F.PIRANI et al. International Review in Physical Chemistry 25 (2006) 165
NEUTRAL-NEUTRAL
PREDICTION of POTENTIAL PARAMETERfor UNKNOWN SYSTEMS
hard interactionssoft interactions
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
3 100
4 100
5 100
6 100
7 100
8 100
9 100
101
1000 10000
O(3P)-O(1D)
O(1D)-O(1D)
O(3P)-O(1S)
O(1D)-O(1S)
O(1S)-O(1S)
TEMPERATURE [K]
COLLISION INTEGRALSCOMPARISON between CLASSICAL and PHENOMENOLOGICAL APPROACHES
LARICCHIUTA et al. (2008)
CAPITELLI et al. (1972)
phenomenological approach
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
INELASTIC (CHARGE TRANSFER) DIFFUSION-TYPE COLLISION INTEGRALs for N*-N+ INTERACTIONs
involving HIGH-LYING EXCITED STATES
Dependence of diffusion-type collision integrals for the interaction N+(3P)-N on the principal quantum number of the atom valence shell electrons, n, at T=10,000 K (different electronic states of N, arising
from the same electronic configuration have been considered. n=2 N(2p3 4S,2D,2P), n=3 N(2p23s 2P,4P;), n=4 N(2p24s 2P,4P;), n=5 N(2p25s 2P,4P;)
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
0.0
10.0
20.0
30.0
40.0
50.0
60.0
0.0 1.0 2.0 3.0 4.0 5.0
ELECTRONIC LEVEL EIGENVALUE [eV]
inelastic
elastic
effective
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
0.0 1.0 2.0 3.0 4.0 5.0
ELECTRONIC LEVEL EIGENVALUE [eV]
inelastic
elastic
effective
EFFECTIVE DIFFUSION-TYPE COLLISION INTEGRALSfor N-N+ INTERACTIONS involving LOW-LYING EXCITED STATES
ELASTIC CONTRIBUTION from PHENOMENOLOGICAL POTENTIALS andINELASTIC CONTRIBUTION from CHARGE-EXCHANGE CROSS-SECTIONS
T = 10,000 K
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
a) photodissociation of H2(), D2(), HD() and H2+()
b) heavy particle collision cross sections : H2(), D2() from recombinationc) H2() formation on graphited) heavy particle collision cross sections for O-O2 and N-N2 : fitting relationsd) collision integrals for O-O and O-O+ interactionse) collision integrals for N-N and N-N+ interactions: a phenomenological
approach
a) thermodynamic properties of atomic hydrogen plasmab) transport properties of atomic hydrogen plasma: cut-off criteriac) negative ion source modeling
ELEMENTARY PROCESSES
OUTLINE
THERMODYNAMICS, TRANSPORT AND KINETICS OF PLASMAS
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
• (curve a) energy levels from the Debye-Hückel potential [23]
• (curve b) energy levels from the Coulomb potential
• (curve c) only hydrogen ground state (fH= 2, cp,int(H)=0).
For curves a and b the number of l evels is truncated by using the Griem cut-off, calculatedself-consistently with the plasma composition.
THERMODYNAMIC PROPERTIES for ATOMIC HYDROGEN PLASMA
M. Capitelli, D. Giordano, G. ColonnaThe role of Debye-Hückel electronic energy levels on the thermodynamic properties of hydrogen plasmas including isentropic coefficientsPhysics of Plasmas 15(8) (2008) 082115
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
Internal partition function Internal specific heat
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
internal state contribution
reaction contribution
CONTRIBUTION TO SPECIFIC HEAT
Frozen Specific Heat Reactive Specific Heat
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
HYDROGEN MIXTURE ISENTROPIC COEFFICIENT
Total Frozen
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
GROUND STATE METHODS
DEBYE HÜCKEL CRITERION
CONFINED ATOM APPROXIMATION
internal energy = 0
particle density
IN ANY CASE
DRASTICALLY DECREASES
INCREASING PRESSURE
or ELECTRON DENSITY!!!
TRANSPORT PROPERTIES for ATOMIC HYDROGEN PLASMA : CUT-OFF CRITERIA
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
1018
1020
1022
1024
1026
1 104
2 104
3 104
4 104
5 104
nH
, m
-3
Temperature, K
p=1000atm
p=1atm
p=100atm
EFFECT of DIFFERENT CUT-OFF CRITERIA on ATOMIC HYDROGEN NUMBER DENSITY
GROUND-STATE
DEBYE-HUCKEL
CONFINED-ATOM
Trampedach et al. Astrophys. J. (2006)
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
10
0
10
1
10
2
10
3
10
4
10
5
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
Temperature, K
H
+
-H(n=12)
H
+
-H(n=6)
H
+
-H
+
(1atm)
H
+
-H
+
(1000atm)
H
+
-H(n=1)
H
+
-H
+
(100atm)
σ
2
Ω
(1,1)*
, A
2
10
0
10
1
10
2
10
3
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
Temperature, K
σ
2
Ω
(2,2)*
, A
2
H
+
- ( =12)H n
H
+
- ( =6)H n
H
+
- ( =1)H n
H
+
-H
+
(1000 )atm
H
+
-H
+
(100 )atmH
+
-H
+
(1 )atm
DIFFUSION-TYPE COLLISION INTEGRALS VISCOSITY-TYPE COLLISION INTEGRALS
COLLISION INTEGRALs for H(n)-H+ INTERACTIONs compared withCOULOMB COLLISION INTEGRALs
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
• case USUAL EES considered as independent chemical species BUT EES collision integrals set equal to
ground state ones
• case ABNORMAL EES considered as independent chemical species withtheir own collision integrals
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
0
1
2
3
4
5
6
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
Temperature, K
λ
h
, / *W m K
=1000p atm
=1p atm
=100p atm
0 10
0
5 10
-5
1 10
-4
1,5 10
-4
2 10
-4
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
η
, /( * )Kg m s
, Temperature K
=1000p atm
=1p atm
=100p atm
EFFECT of DIFFERENT CUT-OFF CRITERIA on TRANSPORT PROPERTIES of HYDROGEN PLASMA
including ABNORMAL TRANSPORT CROSS SECTIONs for EES
HEAVY PARTICLE THERMAL CONDUCTIVITY VISCOSITY
GROUND-STATE
DEBYE-HUCKEL
CONFINED-ATOM
D. Bruno, M. Capitelli, C. Catalfamo, A. Laricchiuta Physics of Plasmas (2008) in press
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
0
1
2
3
4
5
6
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
λ
r, / *W m K
, Temperature K
=1p atm
=100p atm
=1000p atm
EFFECT of DIFFERENT CUT-OFF CRITERIA on TRANSPORT PROPERTIES of HYDROGEN PLASMA
including ABNORMAL TRANSPORT CROSS SECTIONs for EES
GROUND-STATE
DEBYE-HUCKEL
CONFINED-ATOM
0 10
0
2 10
-1
4 10
-1
6 10
-1
8 10
-1
1 10
0
0 10
0
5 10
-2
1 10
-1
1,5 10
-1
2 10
-1
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
λ
int
, / * W m K CA
λ
int
, / * W m K SCCP
, Temperature K
=1000p atm
=100p atm
=1p atm
REACTIVE THERMAL CONDUCTIVITY INTERNAL THERMAL CONDUCTIVITY
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
3 CRITICAL AREAS (“remote” source)• Source chamber (driver): ICP (transformer) heating at high RF power No sheath losses Hot electrons• Expansion region: H2 vibrational excitation• Extraction region: Magnetic filtering Cold electrons H- production (surface/volume) Electron removal
Length 0.35 m
Radius 0.2 cm
Input Power 170 kW
Current coil 100 A
Frequency 1 MHz
Pressure 0.6 Pa
Max magnetic field 160 G
Extraction grid potential -20 kV
RF-ICP NEGATIVE ION SOURCE
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
10-19
10-17
10-15
10-13
10-11
10-9
10-7
10-5
0,001
0,1
0 2 4 6 8 10 12 14
H2
(v) VDF
Vibrational level v
Boltzmann Tg VDF
€
Nv = N 1 − e−E v / k BTg
[ ]e−E v / k BTg
€
Ev = hω(v +1 / 2) − hωxe (v +1 / 2)2H2(v)
vibrational distribution function
(*) J. R. Hiskes et al., J. Appl. Phys. 53(5), 3469 (1982)(**) O. Fukumasa, K. Mutou, H. Naitou, Rev. Sci. Instrum. 63(4), 2693 (1992)
1015
1016
1017
1018
1019
1020
0 3 6 9 12 15
(eV + EV)(eV + EV) + AV(eV + EV) + AV + sV(eV + EV) + AV + sV + (Vt + VT)
vibrational distribution function (m
-3 )
vibrational level v
EXPANSION REGION: H2() EXCITATION
H2()VIBRATIONAL
DISTRIBUTION FUNCTION
CRP (COORDINATED RESEARCH PROJECT), IAEA MEETING “ATOMIC and MOLECULAR DATA for PLASMA MODELING” VIENNA, NOVEMBER 2008
FUTURE PERSPECTIVEs
a) elementary gas-phase processes involving Caesium b) direct approaches for gas-phase recombination
c) H2() formation on caesiated surfacesd) approaches for collision integral calculation
of highly excited states interactions
a) transport properties of air plasma with electronically excited statesb) transport of radiation
c) negative ion source modeling improvements
ELEMENTARY PROCESSES
THERMODYNAMICS, TRANSPORT AND KINETICS OF PLASMAS