EPP ZS 2023 3AAA

Recombination … electron - ions

AB+ e-

Mliečna dráha
Recombination

A+ e -

Radiative recombination
Ar+ + e- → Ar + hn AB+ e-
Dissociative recombination
AB+ + e ➔A + B

O2+ + e ➔ O+O
Processes: at low impact energies
Elastic scattering
AB + e AB + e
Electronic excitation
AB + e AB* + e
Vibrational excitation
AB(v”=0) + e AB(v’) + e
Rotational excitation all go via (AB-….)** .
AB(N”) + e AB(N’) + e
Intermediate negative ion
Dissociative attachment
AB + e A− + B
A + B−
Impact dissociation
AB + e A+B+e
Dissociative recombination Go via (AB….)** .
AB+ + e A+B Intermediate neutral molecule
Vibrational excitation, deexcitation and dissociation in H2+ - e- collisions

H2 +
Electron –ion recombination
H+ + e- ➔ products
H2+ + e- ➔ products
H3+ + e- ➔ products
H5+ + e- ➔ products

92.1% of nucleons in the universe are protons

7.8% are helium nuclei !
Recombination processes in plasma
Binary recombination  [cm3s-1]

H + + e → H + hn RR
radiative recombination

+
O2 + e → O + O DR dissociative recombination

we can write
for [O2+ ] = ne +
dne d [O2 ] +
= = − [O2 ]ne = −ne
2

dt dt

Fe7+ + e → Fe6+ DiR dielectronic recombination

Recombination processes in plasma

Ternary electron assisted recombination

dne d [ Ar + ]
Ar + + e + e → Ar + e = = − K e [ Ar + ]ne = − eff [ Ar + ]ne
2

dt dt
Collisional Radiative Recombination
KCRR [cm6s-1]  eff = K e ne
CRR

Ternary neutral assisted recombination

dne d [ Ar + ]
= = − K M [ Ar + ]ne [ He] = − eff [ Ar + ]ne
Ar + + e + He → Ar + He dt dt

KM [cm6s-1]  eff = K M [He]

Electron - Ion Collision
H+ + e-➔~ very slow recombination  −
H+ + e-➔ H + hn RR
H+ + e- + e- ➔H + e- ternary CRR

H2+ + e- ➔ H + H,
Dissociative Recombination - DR
H

H2 + H2*

Electron collisions with H2+ - how to describe ????

 Intermediate neutral molecule
e- + AB+

Capture
Autoionization

AB* resonant state(s) predissociation

To get high recombination rate, we need

(a) efficient capture
(b) predissociation faster than auto-ionization
Electron-cold molecular ion reaction:
Dissociative Recombination
Go via (AB….)** .
V AB+ + e-  A(n) + B(n’) + KER

HD+ (2p )
u
AB**
Indirect process Direct process

AB+
Interference
Rydberg state
HD+ (2 +)
e-
g

Kinetic
Energy
Release

A(n)+B(n’)

R
 Recombination of H3+ : No ion-neutral crossing

V AB+ + e-  A(n) + B(n’) + KER

AB** HD+ (2p )

u

Indirect process
Indirect process Direct process

AB+
Interference
Rydberg state
HD+ (2 +)
e-
g

Kinetic
Energy
Release

A(n)+B(n’)

R
 A+ + B
A+ + B
potential energy, U(r)

potential energy, U(r)

2 3
3
1 2
e
0 e 1

0
0 (AB*)rep.
(AB*)rep. A* + B*
A* + B*
R AB* Ryd.
Rc s

internuclear separation, R internuclear separation, R

Direct mechanism Indirect mechanism

Resonances Electron - Ion Collision- Recombination
H2+ + e-

H + H(n)
SA and absorption experiments (CRDS)

O2+ + e-
2001
He2+ 2004
2019
Theoretical background
Dissociative Recombination without a Curve Crossing
Theory predicted: DR rate coefficient is vary small  10-11 cm3s-1

HeH+ and HCO+ ions-

examples of a non-crossing case.
However, experiments gave
α  210-8 and α  2 10-7 cm3s-1
A new mechanism has been proposed!

Multi-step indirect
dissociative recombination
(“tunneling mode” recombination)

hartree (symbol: Eh or Ha), also known as the Hartree energy, 27.211386245988(53) eV

Recombination HeH+
Concept of recombination rate coefficient (plasma binary reactions)

at T
e A+
T

e- + A+ → products
dNA/dt= -neNA
RECOMBINATION RATE COEFFICIENT
= (T)
=  (v) =  (e)
Collision rate coefficient, Recombination rate coefficient
 = < ur>
H3+ + e- → H + H2; 3H x
+ + +
Single collision + - + +
+ H
I0 + H3+ + I
+ +
vr +
e- e- e- H3+
I(x)
H2
I=I0exp(-nix)
(vr) recombination cross section
k(T)=<v>
Multiple collision

H3 + 10
10

T
ne [cm ]
-3

9
10

e- 10
8

time

k(T)
recombination rate coefficient
dni/dt=-knine
2019
Recombination HeH+
2019
Recombination HeH+

2020
Cross sections measured obtained in
Ion Storage Ring experiments

Quo vadis??
HD+ + e- Dissociative recombination
Dissociative recombination HD+

Scan of electron ion relative energy E

Electron temperature kTPer=4meV (30meV for E>0.3eV)
kTPar=0.1meV
Energy resolution ~4….8 meV (E< 0.08eV)
Absolute accuracy of cross section ca. +- 30%
Recombination H2+
Recombination NO+
Recombination of H3+

e-

H3++ e- → H+H+H
p+ → H2+H
e- e- → H3* (?)
p+ p+
Tunneling dissociative recombination

H3+
Tunneling dissociative recombination

H3+
Dissociative recombination of H3+ .
Relevant potential curves

3-body decay

2-body decay
 Dissociative recombination of H3+

Remote curve crossing

H3 +

H3* Electron capture via

Jahn-Teller coupling of
electronic and ro-vibrational
75% motion

25%

Symmetric deformation Prototype system for electron

capture and dissociation
mechanisms in polyatomic species
Equilateral
Three atomic ions Dissociative recombination of H3+
Prototype system for electron
capture and dissociation
mechanisms in polyatomic species

H3+

H3*

75%

25%

Electron capture via

Jahn-Teller coupling of
Symmetric deformation electronic and ro-vibrational
motion
Equilateral
2004 - 2007
 e- + H3+

Capture
Autoionization

H3* resonant state(s) predissociation

To get high recombination rate, we need

(a) efficient capture
(b) predissociation faster than auto-ionization
 Cosmic-ray ionisation rate g3x10-17s-1

Formation
hn H2
H2 H2 + H3 +

d[H3+]/dt~ g.[H2]

a) DENSE CLOUDS:

H3+ + CO d[H3+]/dt ~ -kCOx[H3+]x[CO]

(kCO=2x10-9cm3s-1)

[H3+]=g/kCO . [H2]/[CO]= ~1x10-4cm-3

~OK with observation

Cosmic-ray ionisation rate g3x10-17s-1

Formation
hn H2
H2 H2 + H3 +

d[H3+]/dt~ g.[H2]

b) DIFFUSE CLOUDS:

H 3+ + e - d[H3+]/dt ~ - DR [H3+][e-]

DR=2x10--7cm3s-1 x(T/300)-0.65 (the value from 2005)

[H3+]=g/DR . [H2]/[C]= ~1x10-7cm-3

~ NO with observation
… history is repeating itself …. … One remaining
problem is to understand
the plasma afterglow
experiments.
H 3+ + e−  H + H 2 , 3H RSDM DR
2012 2013
Plasma in TDE

(T=300 K) +
D3 H3
+
SA
A FALP

+
-6 A - M.A. Biondi
=(−) 

3
10 MB

+
B - K.B. Persson

+ FALP - H
Stor. Ring
[cm s ]

C - J.A. Mac Donald

3 -1

IR-CRDS
Other methods

AISA - H
D - N.G. Adams
E,F - A. Canosa
F (2) (2) H,G,I
O - D. Smith
C I J

D3
N M J - T. Gougousi
-7 K
10 (1) K - S. Laube
E L
J - H. Hus
I M


- M. Larson
+
D3 N
M - D. Mathur
B O
P - T. Amano
1955 D L H (1)
(1) - P. Van der Donk
P
-8 (2) - n=0
10 G (1)
- n>0

1970 1975 1980 1985 1990 1995 2000 2005 …. many times it was concluded,
that the task was finished….

Doubts 2011
“Presently no rate coefficient measurement
with a confirmed temperature below 300 K exists“.
Petrignani et al. Phys. Rev. A (2011)

and … history repeated itself .

M. Larsson et al, CP Letters (2008)
… and the caravan is….onthere
its is
way….
Calculated life time from Slava
+
Slava 30 08 07 H +e → H3
*
3

Dear Chris and Juraj,

I'm sending you the plot with the time delay calculation for two different
symmetries that correspond to the lowest rotational states of ortho- and
para-H3. In the both cases, rotational autoionization is important.
Since time delay is proportional to lifetimes (at maxima of the time delay
spikes), I scaled the spectrum in such way that one can read the lifetime
directly in ps (again at the tops of the spikes).
JURAJ, you probably don't want to go into details of these calculation. To
obtain the lifetime of one of these resonances you just look what is the
value of the corresponding maximum. This will give you the lifetime in ps.
You don't need to estimate the width.
The important message here to me is that "typical" lifetimes associated with
rotational autoionization are larger than 10ps. Thus, our previous estimation

+
H +e  H → * of the three body coefficient should be corrected and now it gives a value
close to the one that Juraj has derived from the experiment.
Notice that the experimental temperature is close to the second ionization
3 3 limit for para-H3+ . This is the (21) rotational state. The lifetimes there
are very long >100ps. Another interesting feature: the perturbers at 40, 85,
120 and 150 cm-1 in the red curve. They are due the higher rotational states
(31). Due to their presence, the formation of rotational states (21) is
enhanced.
Slava 30 08 07

Dear Juraj and Chris, I'm sending you the figure with the DR
probabilities for two different symmetries (red and black
curves). The red curve corresponds to the rotational
autoionization region. Fro this figure you can have an idea
about the widths of the resonances. With best wishes, Slava
Recombination rate coefficients
 The battle ship enters the stage

H3+ is Cryo-SA-CRDS
The experiments - FALP, AISA, TDT+CRDS
fundamental

Plm
Cryo-NIR-CRDS

AISA Cryo-FALP

43
12/6/2023 3:47:20 PM
Pulsed (stationary) afterglow

Discharge pulse
microwave, UV, x-ray, e-beam

Measure ne(t)

t
dne
Get: = − ne + (diffusion)
2

dt
Plasma chamber
ne 0
He: ~ 1 –20 Torr ne (t ) =
Ar: 10 to 30 % 1 +  ne 0t
+ molecules
 We measure effective – apparent binary recombination rate coefficient

12
10 Quasineutral H3+ dominated plasma
ptot= 6,2 Torr
14 -3
[H2] = 4×10 cm
[H3 ] [cm ]
-3

11
10

dne ne
+

10
10 = − eff ne −
2

dt L
9
10
0.0 500.0µ 1.0m
1 1
t [s] = + t
[ H 3+ ] [ H 3+ ]0
3.00E-010
2.50E-010
2.00E-010
1.50E-010
1.00E-010
5.00E-011
0.00E+000
0.00 500.00µ 1.00m
t [s]
 We measure effective – apparent binary recombination rate coefficient

12
10 Quasineutral H3+ dominated plasma
ptot= 6,2 Torr
14 -3
[H2] = 4×10 cm
[H 3 ] [cm ]
-3

11
10

dne ne
= − eff ne −
+

10
2

L
10

dt
9
10
0.0 500.0µ 1.0m
1 1
t [s] = + t
[ H 3+ ] [ H 3+ ]0
4
cm ]
3

3
-11
1/[H 3 ] [10

2
+

0
0.00 100.00µ 200.00µ
t [s]
Decay in diffusion and recombination governed plasma

dne Da
= − ne − 2 ne
2

dt 
1 exp (nt ) − 1 1
=α + exp (nDt )
ne nD n0
10 +
10 He 2 diffusion
+
He 2
ne [cm ]
-3

+
9 Ar
10

+
+ O2
8
O 2 diffusion
10

0 10 20 30 40
time [ms]
Decay in diffusion and recombination governed plasma
dne Da
= − ne − 2 ne
2

dt 
1 exp (nt ) − 1 1
=α + exp (nDt )
ne nD n0
Limit for t -->0 Limit for large t

1 (1 + nDt ) − 1 1 α 1
=α + (1 + nDnt ) 1
= ( + ) exp (nDt )
0

ne nD n0
n e n D n0
1 1
= αt + (1)
ne n0
 Experiment:
11 P = 3300 Pa, T = 300 K
10 16 -3 14 -3
[H2] = 2×10 cm , [Ar] = 6.7×10 cm
+
H3 fit diffusion
10
10
n (cm )
-3

Model:
9
10 -7 3 -1 -6 3 -1
H3+ = 2×10 cm s , H5+ = 2×10 cm s
+ +
H3 H5

8
10

7
10
0 200 400 600 800
t (ms)
Srovnani modelu a experimentu. Pocatecni podminka: [H3+] = ne = 2×1011 cm-3.
 Experiment:
P = 3300 Pa, T = 300 K dne
= −[1n1 (t ) +  2 n2 (t )]ne
11
10 16 -3 14
[H2] = 2×10 cm , [Ar] = 6.7×10 cm
-3

+
H3 fit diffusion dt
10
10   eff (t ) = [1 f1 (t ) +  2 f 2 (t )]
f1 + f 2 = 1
n (cm )
-3

9
10

8
10 Model:
-7 3 -1 -6 3 -1
H3+ = 2×10 cm s , H5+ = 2×10 cm s
+ + m
H3 H5 He
7
10
0.8
fractions

0.4

0.0
0 200 400 600 800

Model + data. Pocatecni podminka: ne = Hem = [H3+].

Poznamka. Namerene τ difuznich ztrat 1.6 ms. Teoreticke τ pri danem tlaku je 1.8 ms (odpovida cca 4×1010
cm-3 koncentraci necistot (pri 2×10-9 cm3s-1 rychlosti reakce H3+ s necistotami). Namerena koncentrace vody
[H2O] = 5×1010 cm-3 ([He] = 8×1017 cm-3).
 If there are 2 or more ion species, the fast recombining
species disappears first
dne
= −[1n1 (t ) +  2 n2 (t )]ne
dt
  eff (t ) = [1 f1 (t ) +  2 f 2 (t )]
f1 + f 2 = 1
Diffusion and recombination dne = − n 2 − Da n 1 exp (nt ) − 1 1
=α + exp (nt )
e 2 e
dt  ne ν n0

+ - 9 Torr, NH = 0.17 sccm

16 NH4 .(NH3)2 + e 3

9 Torr, NH = 0.44 sccm

10 3

9 Torr, NH = 0.72 sccm

3

11.5 Torr, NH = 1.4 sccm

15 3

10
ne [m ]
-3

0 1 2 3 4 5
14
10
-15
1,5x10

1/ne [m ]
-15

3
1,0x10
13
10
-16
5,0x10

0,0
12
10
0 1 2 3 4 5 6 7 8 9
TRANSITIONAL REGION
L [cm]

J. Glosík, G. Bánó, R. Plašil, A. Luca, P. Zakouril,

Study of the electron ion recombination in high pressure flowing afterglow. Recombination of NH4+.(NH3)2,
International J. Mass Spectrom., 189, 103-113 (1999)
Advanced analyze O2+
dne / dt = −[O2+ ]ne −n D ne −n R ne = −ne2 −n D ne −n R ne
1 1
− =  (te − t0 ) − ne ´/ ne2 =  + (n D + n R ) / ne
ne n0

10 +

(-ne/ne-nD/ne)[cm s ]
10 He2 diffusion -7

3 -1
4x10
+ +
He2 O2
ne [cm ]
-3

+
9 Ar
10
-7
2x10
2
'
+
+ O2
8
O2 diffusion
10

0
2 4 6 8 10
0 10 20 30 40 -9 3
1/ne [10 cm ]
time [ms]
Stationary afterglow (M. Biondy, R. Johnsen)

M.T.Leu, M.A. Biondy, R. Johnsen

recombination of H3+ and H5+

mw SA

R. Johnsen N4+ recombination

at 300-800 Torr a= 2.6x10-6cm3s-1

High pressure SA
RF probe, spark discharge
 ADVANCED INTEGRATED STATIONARY AFTERGLOW
Exp. No.1
AISA

PULSED STATIONARY AFTERGLOW

20-100ms decay

Langmuir probe Ø 14mm

AISA Window Heating / Cooling system
He
Ar Auxiliary
flow in Probe
H2
QMS
QMS
Magnetron
2.45 GHz
0..30 W
0..5 ms
25 Hz

40 cm diameter
UHV - 10-9 Torr flow out
Turbo Pump
Baratron
External magnetron
2 Torr of He/Ar/H2 10 cm

Turbo Pump
CALCULATION OF PLASMA DECAY IN CYLINDER

DIFFUSION AND RECOMBINATION

D=60 ms, =1x10-7cm3s-1 and =5x10-9cm3s-1
e-2 Diffusion in Cylinder Time= 8.10e-3
u
R[cm] 40. a
11 at the probes location j b max 1.18
10 0.0 o k c x: 1.15
w: 1.10
5.0 35. v: 1.05
x u: 1.00
10 m a t: 0.95
-9 3 -1 30. s: 0.90
10 =5x10 cm s 15 r: 0.85
10 q: 0.80
n [cm ]

25. p: 0.75
-3

o: 0.70
h n: 0.65
m: 0.60
20.

Z
l: 0.55
-7 3 -1 w k: 0.50
10
9
=1x10 cm s j: 0.45
15. i: 0.40
e h: 0.35
u g: 0.30
10. r i f: 0.25
v e: 0.20
a p
t d: 0.15
8
10 5. n
q
s c:
b:
0.10
0.05
l
g a: 0.00
a a
f min 0.00
0. d
a
0 10 20 30 40 50 60
-0.1 -0.05 0. 0.05 0.1 0.15 0.2 0.25 0.3
time [ms]
R

Time evolution Spatial distribution

after 8 ms
RECOMBINATION AND DIFFUSION
in He/O2+/e- plasma (2 Torr, D~60ms)
(O2+The decay of afterglow plasma
, 300K)=
different 2x10
dominant ions
-7in three3sdifferent
He , Ar ,cm
O .
2
+ +
2
+
+three
O2
-1 condition with

+ −
O + e  neutral
10 +
10
2 products He2 diffusion
+
He2

d [O +2 ] ne

ne [cm ]
= − [O 2 ]ne −

-3
+
+ 10
9 Ar

dt D +
+ O2
8
O2 diffusion
10
Only recombination:

1 / ne = 1 / ne 0 + t
time ms
0 10 20 30 40
time [ms]

Only diffusion With recombination and diffusion

1
ne = ne 0 exp( − t ) ne =
D 1
 D exp ( t /  D ) + exp ( t /  D )
n0
 Formation of H3+ in He/Ar/H2 mixture

He He2 99/1/<0.01% (1017/1014/1011-14)

microwave discharge

+
He+ Ar
Ar H2 H2
Hem Ar + +
ArH , H2 +
H3+
Ar+
+e-(300K)
Arm hn
H2+
HeH+
H+
+He+He

FORMATION:
Ion molecule reactions during the early afterglow
 Formation of H3+ in He/Ar/H2 mixture
microwave discharge

He+ 1017/1014/1011
Ar H2 H2
Hem Ar + ArH+, H2+ H3+
Changes due to the ion molecule reactions during the early afterglow
Ar+
7
10 Ar
+

Arm 10
6

He/Ar 10
5
ArD
+

+ + +
C H2O N2 +

H2 + 10
4
CO2

5
1x10 Ar
+

Intensity (a.u.)
He/Ar/H2 8x10
4

4
+
H3
H3+ +
4x10 ArH
+
H3O
0
+
D3

He/Ar/D2 D3+
5
2x10 +
ArD
+
Ar
5
1x10
+
DH2O + +
DN2 ArD3
0
0 10 20 30 40 50
mass [amu]
VT - AISA dni/dt=-nine He/Ar/H2
AISA
(T)
H3+
T
e-

40 cm diameter
UHV - 10-9 Torr
External magnetron
2 Torr of He/Ar/H2 PULSED STATIONARY AFTERGLOW
20-100ms decay ne(), ni()


VT - AISA 2 Torr of He/Ar/H2

AISA
Formation of H3+ in He/Ar/H2 mixture
He+ Calculated from kinetic model
Hem, Arm Ar, H2 H2 H2
Ar + ArH+, H2+ H3+
Ar+ H3+
ne simulation + integral spectrum
5 H3
10 1,5x10
10 Ar
+

5
1,0x10
+
4
ArH
5,0x10 +
Ar
+
9 +
H3O
10 He H3
+

Intensity [au]
+ 0,0
Intensity [au]

ArH
+
He2 + 5 +
integrated from
H3O 1,5x10 H3 simulation spectrum
8 5
10 1,0x10 +
ArH
experiment 4
+
10 Ar 5,0x10 + Ar
+
10 +
He He+2 H3O
+ 0,0
H3
+
integrated from time
5
+ 1,5x10 H3 resolved spectrum
9
ArH
10 5
1,0x10
4 +
5,0x10 + Ar
+ ArH
H3O
+ H3O
8
10 0,0
0,1 1 10 100 0 5 10 15 20 25 30 35 40 45
time [ms] mass [amu]
Formation of H3+ in He/Ar/H2 mixture
He+
Hem, Arm Ar, H2 H2 H2
Ar+ ArH+, H2 +
H3+
Ar+

Calculated from kinetic model +

H3 diffusion

5
ne simulation + integral spectrum 10
5 H3
10 1,5x10
10 Ar
+
11 -3
5
1,0x10 [H2]=6.7x10 cm

Intensity [au]
+
4
ArH
5,0x10 +
Ar
+
9 +
H3O
10 He H3
+
+
Intensity [au]

+ 0,0
Intensity [au]

ArH
integrated from 4 ArH
+
He2 H3O
+ 5 + 10
1,5x10 H3 simulation spectrum
10
8

+
experiment
5
1,0x10
4
5,0x10
ArH
+
H3+
10
10
Ar
+
H3O
+ Ar
+
k2
He He+2 +
H3
+ 0,0 Ar
+
integrated from time 3
+
5
1,5x10 H3 resolved spectrum 10
ArH
10
9
5
k1
1,0x10
4 +
0 5 10 15 20 25 30 35 40 45 50 55 60
5,0x10 ArH
H3O
+ H3O
+ Ar
+
time[ms]
8
10 0,0
0,1 1 10 100 0 5 10 15 20 25 30 35 40 45
time [ms] mass [amu]

Measured time evolution

Time resolved mass spectra
Rates of the decays are dependent on [H2]

+
H3 diffusion

5
10
+ 11 -3
H3 (nH =1.010 cm )
Intensity [au]

4
10 ArH
+

+ 11 -3
H3 (nH =2.610 cm )
2
+ k2
Ar
3 + 11 -3
10 k1 H3 (nH =6.710 cm )
2

0 5 10 15 20 25 30 35 40 45 50 55 60
time[ms]
 dne
Time resolved mass spectra = −[1n1 (t ) +  2 n2 (t )]ne
dt
  eff (t ) = [1 f1 (t ) +  2 f 2 (t )]
f1 + f 2 = 1
OBSERVED DEPENDENCE ON [H2]!!

+
H3 diffusion H3+ fraction
1,0

5 11 -3
10 [H2] [10 cm ]

f
0,5 1.0
+ 11 -3
H3 (nH =1.010 cm ) 2.6
6.7
Intensity [au]

diffusion
5
10

Intensity [au]
4
10 ArH
+ +
H3

+
4 H3
+ 11 -310
H3 (nH =2.610 cm ) ArH
+

2
+ k2 +
H3
Ar
3
10 Ar+
3 + 11 -3
10 k1 H3 (nH =6.710 cm ) 0 10 20 30 40 50 60
2

time[ms]
0 5 10 15 20 25 30 35 40 45 50 55 60
time[ms]

It is only qualitative information, not sufficient to obtain 

Correction to ion composition 1

f=H3+/ions
1,0
11 -3
[H2] [10 cm ]
f

0,5 1.0
2.6
6.7

diffusion
Intensity [au]

5
10
+
H3 - 1.0

+
10
4 H3 - 2.6
+
ArH

+
3 H3 - 6.7 1,0
10 Ar+

0 10 20 30 40 50 60
t [ms]
f
calculated data
0,5 11 -3
[H2] [10 cm ]
1.0
2.6
6.7

0,00 0,02 0,04 0,06 0,08 0,10 0,12

11 -3
(tx[H2]) [1x10 s cm ]
2009
Next lecture: SA and absorption experiments (CRDS)
 Temperature dependence

Ne2+

Multiple collision

Ne2+ Ne3+
T
e-
k(T)
recombination rate coefficient
In-situ satellite data

[cm3s-1 ]
10-6 NO+ O2+

The points indicated by blue

triangles are the (NO+) deduced -0.85
from in-situ satellite data by
(NO+ ) ~ Tg,e

M. R. Torr, J. P. St-Maurice and D. G. Torr,

J. Geophys. Res., 82 (1977) 3287.

The agreement between these data and

the laboratory data is remarkable.

10-7 -0.65
(O2+ )~ Tg,e

100 200 500 1000 2000

T g ,T e [K]
 1.6
+
H +e → H *
62 K
72 K
eff (10 cm s )
3 -1

1.2
100 K

0.8
3 3
-7

0.4
+
Ar
0 5 10 15 20 25
17 -3
[He] (10 cm )

-5
10 -3
ne (cm )
+ 10
H3 5×10 SA-CRDS
77 K
+ 9
H3 2×10 Cryo-FALP I
-6
10 + 9
H3 2×10 Cryo-FALP II
eff (cm s )
3 -1

-3
ne (cm )
-7 10
10 bin DR
Cao <10
+ + +
(N2, O2, NO )
+ 9
Ar 0.4-1.5×10
+ 9
Ar 2.0×10
-8
10 E-CRR(ne0)
corrected for E-CRR
He-CRR= (eff-KE-CRRne)

17 18 19 20 21
10 10 10 10 10
-3
[He] (cm )
 1.6 -6
62 K 10
300 K
72 K
eff (10 cm s )
3 -1

1.2 17 -3
[He] = 2.1×10 cm , [H2] varies
100 K
-3
[He] varies, [H2] = 2×14 cm
0.8 bin + F
-7

F

eff (cm s )
0.4

3 -1
+ -7
Ar 10
A B
0 5 10 15 20 25 bin
17 -3
[He] (10 cm )

2
effH

e
effH



AT BT C
-8
10 14 15 16 17 18 19 20 21
10 10 10 10 10 10 10 10
-3
[H2],[He] (cm )
-5
10 -3
ne (cm )
+ 10
H3 5×10 SA-CRDS
77 K
+ 9
H3 2×10 Cryo-FALP I
-6
10 + 9
H3 2×10 Cryo-FALP II
eff (cm s )
3 -1

-3
ne (cm )
-7 10
10 bin DR
Cao <10
+ + +
(N2, O2, NO )
+ 9
Ar 0.4-1.5×10
+ 9
Ar 2.0×10
-8
10 E-CRR(ne0)
corrected for E-CRR
He-CRR= (eff-KE-CRRne)

17 18 19 20 21
10 10 10 10 10
-3
[He] (cm )
 If there are 2 or more ion species, the fast recombining
species disappears first
dne
= −[1n1 (t ) +  2 n2 (t )]ne
dt
  eff (t ) = [1 f1 (t ) +  2 f 2 (t )]
f1 + f 2 = 1
Line intensity H3+ High sensitivity required

1eV

+ + +
H3 H2D HD2
p * 22
150
211
150
observed
o
]

Temperature [K]
-1

p 212
100
100 o * 202
Energy [cm

o * 10
o 110
p * 11 o * 111 p 110 50
50 111
p * 101 o

p * 101

0
0 p 00 p * 000 o * 000
Stationary afterglow + Spectroscopic identification of recombining ions
d [ H 3+ ]
= − [ H 3+ ]ne = − [ H 3+ ]2 CRDS
dt

IR-CRDS
Laser absorption spectroscopy

He/Ar/H2
 70 Afterglow Discharge
600 Ortho

population (%)
Para Para Ortho (1,1) +
o-H3 (3,3)
60 +
500 p-H3 (1,1)
Energy (cm )
-1

400 50 o-H3 (1,0)

(3,3) other states
300 (2,1) 40
200 (2,2)
30
100 (1,0) (1,1)

0
(0,0) 20 (1,0)
0 1 2 3
G 10
(3,3)
0

300

TRot-ortho (K)
10
11 300 K
(3,3)
+
H3 200
10 (1,0)
10
n (cm )
−3

100
(1,1) Discharge
9
10
+ Afterglow
H5

10
8
He
m 0 100 200 300
0 200 400 600 800 TKin (K)
t (ms)
Absorption studies
H2D+ (2v2 + v3 ← 0)
H2D+
H 3+
He/Ar/H2/D2 1x10
-8
+
[H3] ~ 6.7×10
10
cm
-3

1x10
-7 a) ortho- b) para- c) para-H2D
+

 [cm -1 ] for H 2O lines

T = 380 K

line
-1
-9 H2O ~1.4 mPa 7241.260(15) cm -8 11 1 20 2 00 0 11 1 10 1 21 2

+
8x10 8x10

cm ]
3
-1
2

-1
 [cm -1 ] for H
7241.12415 cm
-9 -8
6x10 6x10

-8
-9 -8
4x10 4x10

 [10
-9 -8
2x10 2x10

0 0 0
-9 -8

ν = 6491.352(2)
-2x10 -2x10
-1
cm6491.3
7241.1 7241.2 7241.3
wavenumber (cm )
-1
7241.4 6458.9 6459.0 6459.106466.4 6466.5 6491.2 6491.4
7241.260(15) cm-1 Wavenumber [cm
-1
] ν0 = 6491.352(2) cm-1
Combination band
H2D+
D2H+ (v1 + 2v3 ← 0) 0,0
2 n3
n +n
2 3

D2H+ 2 n2+ n

-1
1

obs-calc / cm
2 n2
6 +
a) ortho- b) para- c) ortho-D2H -0,1
2 n2+ n3
20 231 3 10 121 2 00 011 1
4
 [10 cm ]
-1

Schlemmer 2006
Farnick 2002
3 n2
-8

2 present 2006
-0,2
4000 5000 6000 7000
0 -1
wavenumber / cm
+ + +
H3 H2D HD2 6534.3 6534.4 6535.9 6536.0 6536.3
p * 22 -1
150 Wavenumber [cm ]
150
211 ν0 = 6534.377(1) cm-1

+
o

Combination band
]

Temperature [K]
-1

p 212
100
100 o * 202
Energy [cm

* 10

D3 ???
o

o 110
p * 11 o * 111 p 110 50
50 111
p * 101 o

p * 101

0
0 p 00 p * 000 o * 000
 Experiment:
P = 3300 Pa, T = 300 K dne
= −[1n1 (t ) +  2 n2 (t )]ne
11
10 16 -3 14
[H2] = 2×10 cm , [Ar] = 6.7×10 cm
-3

+
H3 fit diffusion dt
10
10   eff (t ) = [1 f1 (t ) +  2 f 2 (t )]
f1 + f 2 = 1
n (cm )
-3

9
10

8
10 Model:
-7 3 -1 -6 3 -1
H3+ = 2×10 cm s , H5+ = 2×10 cm s
+ + m
H3 H5 He
7
10
0.8
fractions

0.4

0.0
0 200 400 600 800

Model + data. Pocatecni podminka: ne = Hem = [H3+].

Poznamka. Namerene τ difuznich ztrat 1.6 ms. Teoreticke τ pri danem tlaku je 1.8 ms (odpovida cca 4×1010
cm-3 koncentraci necistot (pri 2×10-9 cm3s-1 rychlosti reakce H3+ s necistotami). Namerena koncentrace vody
[H2O] = 5×1010 cm-3 ([He] = 8×1017 cm-3).
Recombination
Recombination

300 40

T (K)
st
A 300 A 1 stage
a) H G b) B
nd
2 stage
20 C C Resonator
B G Heating shield
200 0 200 H Discharge tube holder
240 260 280
T (K)

T (K)
time (minutes) 1 2 3
A G H
st
G
100 A 1 stage
nd 100
B 2 stage H
B C B
C Resonator
C
G Heat shield
H Discharge tube holder
0 0
0 100 200 0 100 200
time (minutes) time (minutes)
Recombination
2.0
a) TC = 96 K, TH = 104 K, Tkin = (99 ± 3) K
TC = 21 K, TH = 26.5 K, Tkin = (31 ± 2) K
1.5
absorption (a.u.)

Discharge 100 : PmW = 10 W, D = 15%

1.0 : PmW = 25 W, D = 27%

g: PmW = 10 W, D = 50%
80
0.5 g

Tkin, Trot-para (K)

0.0 60 

0.4 b) TC = 96 K, TH = 104 K, Tkin = (108 ± 7) K

TC = 21 K, TH = 26.5 K, Tkin = (32 ± 3) K 
40
absorption (a.u.)

Afterglow
(250ms)
0.2 20
short discharge
long discharge
0.0 0 20 40 60 80 100
7241.25 7241.30 TH (K)
-1
n (cm )

Examples of H3+ absorption line profiles The dependence of the kinetic temperature (Tkin) of H3+ ions
on the temperature TH (temperature of the discharge tube
holder.
Recombination
10
10
a) TC = 48 K

nH3 (cm )
-3
10
10
P = 190 Pa
9
10

nH3 (cm )
-3
8
10
m 0 1000
He t (ms)

-7 3 -1
10
9
eff = (1.0 ± 0.3)×10 cm s

cm )
2

3
b) T = 119 K
C
P = 900 Pa

-10
1

1/nH3 (10
nH3 (cm )

10
-3

10
0 200 400
t (ms)
m
He
-7 3 -1
9 eff = (2.3 ± 0.1)×10 cm s
10
0 500 1000
t (ms)

Time evolutions of the number densities of the H3+ ions

measured at two different temperatures
 The battle ship enters the stage

The experiments - FALP, AISA, TDT+CRDS +

H3 is
fundamental

Plm
Cryo-NIR-CRDS

AISA Cryo-FALP

84
Charles University Prague 12/6/2023 3:47:20 PM
Different views
& different plasmas H3+ and its interaction with e- is
FUNDAMENTAL
If you understand hydrogen,
you understand all
that can be understood.
(V. Weisskopf & G. Herzberg).
H3+ + e-

DR HeH+ H2+ HD+ H3+ D3+ H2D+ H2D+

y


 Evergreens and Bestsellers
H3+ & D3+
 Formation of H3+ in He/Ar/H2
He He2 99/1/<0.01% (1017/1014/1011-14)
microwave discharge

+
He+ Ar
Ar H2 H2
Hem Ar+ ArH+, H2 +
H3++e-
e-
Ar+ DECAY BY
+e-(300K) RECOMBINATION
Arm hn
H2+
HeH+ 10
10

ne [cm ]
H+

-3
+
+ Ar
H3
+He+He 9
10

8 +

e-
10 O2

Ar+ H3+ 14
12
11
[H2][10 cm ]
-3

1/ne[10 cm ]
10

3
He+ 8 6

-9
30
6
4
FORMATION RECOMBINATION 2
0
0 5 10 15 20 25 30 35 40
Time resolved mass spectra time [ms]