EPP 1AAB 2023

IMR – Ion-Molecule Reactions

+ +
I + AB → C + D

O+ + H2→ OH+ + H
When we were still Barbarians

Paesto Italy

Keď my sme ešte boli Barbari

Paestum
When we were still Barbarians Keď my sme ešte boli Barbari

22-pole trap
10-300 K
14thAugust
2002
Our LAB

FACULTY OF MATHEMATICS AND PHYSICS

TROJA, Praha 8
 Interactions of electron
Rotational and vibrational excitation

Rutherford atom Excitation energies

10-10m

+
10-14m

A shape resonance is a metastable state in which an electron is trapped due the shape of a potential barrier.
Unimolecular reactions A➔P
(A ➔ B+C)

Binary reactions A+B➔P

2A➔P

Ternary reactions A+B+C➔P

(A + B + He ➔ AB + He)
2A+B➔P
3A➔P
 Introduction

IMR – Ion-Molecule Reactions

+ +
A +B→C +D
O+ + H2→ OH+ + H
 Ion-Molecule Reactions
+ +
A +B→C +D
• Experimental evidence down to a few K
• Rate coefficients explained by classical
“capture” models in most but not all
instances.
• ion-non polar (Langevin case)

k L = 2e  2  10 −9
cm3 s-1

• ERIC HERBST
• DEPARTMENTS OF PHYSICS, CHEMISTRY AND ASTRONOMY
• THE OHIO STATE UNIVERSITY
 Ion-mol. r. (cont)
• Ion-polar
kTS = k L [0.62 + 0.4767 x ]
2
k = k [1 + x] → 10 −7 cm3 s −1
LD L
1/ 2

D −1 / 2
x= T
2k BT
+ more complex state-specific models
 Ion Molecule Reactions
Binary reactions of cations
H 2+ + Ar  ArH + + H
+
CH 4 + CH 4 → CH 5+ + CH 3

CH 4
+
+ H 2 → CH 5+ + H H 3+ + HD  H 2 D+ + H 2

+
H3 + CH 4 → CH 5+ + H2 H 2 D + + HD  HD2+ + H 2
+
H 5+ + H 2 → H3 + H2 + H2
HD2+ + HD  D3+ + H 2

Unimolecular reactions

Ternary reactions
 Efficient Low T Gas-Phase Reactions
1. Ion-molecule reactions
2. Radiative association reactions
3. Dissociative recombination reactions
4. Radical-radical reactions
5. Radical-stable reactions
Ea = 0 Exothermic
Endothermic

In areas of star formation, reactions with barriers occur.

 Radiative Association
A + B  AB → AB + h
+ +* +

k1
k ra = k r = K (T )k r ; k r  10 2 s −1
k −1
− ( rA + rB ) / 2
K (T )  T , size, bond engy
Few ion trap measurements by Gerlich, Dunn down to 10 K
By now many more IMR…..

What is the 0 K limit?

What about competitive channels?
 Dissociative Recombination Reactions
+
AB + e → A + B
Studied in storage rings down to “zero” relative
energy; products measured for approx.10 systems
Stationary and Flowing Afterglow plasma
k (T ) = A(T / 300) − n n=0.5, 1.5
−7 3 −1
A  10 cm s
Some systems studied: H3+, HN2+,
HCNH+, H3O+, NH4+, CH5+ ,CnHm+
HeH+, Ar+…..
 Attachment

e + A → A + h−

O2 + e-→ O2-

Anions formation
 Some Conclusions
• 1) Low-temperature chemistry in
interstellar clouds (both gas-phase and
surface) partially understood only.
• 2) Chemistry gives us many insights into
the current state and history of sources
• 3) More work on “cold chemistry” is
clearly needed to make our mirror into the
cosmos more transparent.
 Kinetics of elementary process

Parameters of reactions….

reaction cross section

reaction rate coefficient

Single collision H 2+ + Ar  ArH + + H
x
H2 + H
Ar
vr
H2 + ArH+ H 2+
I0 I
Ar s(vr)
vr Ar
ArH+
Ar
Ar Ar Ar (Ar.H2)+
I(x)
H
reaction cross section I=I0exp(-snArx)

 coll = + −nS = +
−nVrel = + −n 2 = +
−nvs Collisional cross section
=2r+R
dI I
=− = − I coll
dt  coll Vrel
n

I (t ) = I 0 exp( − collt ) = I 0 exp( −sn rel t ) I=I0exp(-snArx)

 Kinetics of elementary process H 2+ + Ar  ArH + + H
H2 +

H2 + ArH+
Single collision s(vr)
vr
Ar Ar Ar (Ar.H2)+

k(T)=<vs>
H
reaction cross section I=I0exp(-snArx)
Multiple collision T22PT = 14 K
@T H2
+

H2+ ArH
+

T ion density
100

T  ~ 35 ms

Ar  ~ 1.5 ms
H2+
ArH+
H2+ Pulse ON (+150/-100V)
k(T)
10
-2 -2 -2 -2 -2 -2
0
reaction rate coefficient 1x10 2x10 3x10 4x10 5x10 6x10

time (s)

d(nH2+)/dt=-k nH2+. nAr nH2+. =(nH2+). 0 exp(-knArt)

Kinetics of elementary process H 2+ + Ar  ArH + + H

Simple description using symbols A+….

for number densities….
d [ A+ ]
= −k BIN [ A+ ][ B ]
[B]>>[A+] dt

Multiple collision T22PT = 14 K

@T H2
+

H2+ ArH
+

T ion density
100

T  ~ 35 ms

Ar  ~ 1.5 ms
H2+
ArH+
H2+ Pulse ON (+150/-100V)
k(T)
10
-2 -2 -2 -2 -2 -2
0
reaction rate coefficient 1x10 2x10 3x10 4x10 5x10 6x10

time (s)

d(nH2+)/dt=-k nH2+. nAr nH2+. =(nH2+). 0 exp(-knArt)

 Binary reactions Reaction rate coefficient
+ +
A + B →C + D [kBIN ] = cm3 s −1

+
d[ A ] +
= −k BIN [ A ][ B ]
dt
Often it is written in simpler form
using A+ instead of [A+]

+
dA +
= −k BIN A B
dt
 + +
A + B →C + D

s(vr) k BIN = k BIN (T )

k(T)=<vrs(vr)>
k =  fT (v).v.s (v)dv = k (T )
v
 H C
H-C + D ➔ ➔ H + C-D
D

H +C

HC HC

D +C
CD
D
H
 Reaction coordinate

Reaction Coordinate
“…..In chemistry, a reaction coordinate is an abstract one-dimensional coordinate which
represents progress along a reaction pathway. It is usually a geometric parameter that
changes during the conversion of one or more molecular entities. In molecular dynamics
simulations, a reaction coordinate is called collective variable. …..”

A +H2 ➔…. ➔C + …..

The ion chemistry of the lower atmosphere
 ……probability of reactive collision Collision rate coefficient -
Techniques for study of IMR – reality Langevin rate coefficient

k(T)=<vrs(vr)> Reaction rate coefficient

kL~10-9cm3s-1
 Dense Interstellar Cloud Cores

10 K

10(4) cm-3

H2 Molecules seen in IR
dominant absorption and radio
emission
sites of star
formation

Cosmic rays create weak plasma

Fractional ionization < 10(-7)
 Cosmic Elemental Abundances
• H =1 • Dust/gas = 1% by
• He = 6.3(-2) mass
• O = 7.4(-4) 1.8(-4) • Gas-phase abundances
• C = 4.0(-4) 7.3(-5) of heavy elements in
clouds reduced.
• N = 9.3(-5) 2.1(-5)
• S = 2.6(-5) 8.0(-8)
• Si = 3.5(-5) 8.0(-9)
• Fe = 3.2(-5) 3.0(-9)
 GAS PHASE INTERSTELLAR/CIRCUMSTELLAR MOLECULES - HIGH RESOLUTION (12/03)
_____________________________________________________________________________________________

H2 KCl HNC NH3 C3S C5 C6H

CH3 HC4CN
CH AlCl HCO H3O+ CH4 CH3OH C7H, C6H2
C8H
CH+ AlF HCO+ H2CO SiH4 CH3SH HCOOCH3
CH3COOH
NH PN HOC+ H2CS CH2NH C2H4 CH3C2CN
H2C6(lin)
OH SiN HN2+ HCCH H2C3(lin) CH3CN C6H2
H2COHCHO
C2 SiO HNO HCNH+ c-C3H2 CH3NC C2H5OH
(CH3)2O
CN SiS HCS+ H2CN CH2CN HC2CHO C2H5CN

CO CO+ C3 C3H(lin) NH2CN NH2CHO CH3C4H

CSi SO+ C2O c-C3H CH2CO HC3NH+ HC6CN
CO2 C4H2 (CH2OH)2
CP H3+ C2S HCCN HCOOH H2C4(lin) (CH3)2CO
AlNC
CS CH2 SiC2 HNCO C4H C5H CH3C4CN?
HF SiCN SiC3 C5N
NO NH2 SO2 HOCO+ HC2CN CH3NH2 NH2CH2COOH?
NaCN CH2CHOH
NS H2O OCS HNCS HCCNC CH3CCH HC8CN
SO H2S MgNC C2CN HNCCC CH3CHO c-C6H6
HCl C2H MgCN C3O C4Si CH2CHCN HC10CN
NaCl HCN N2O NaCN H2COH+ c-CH2OCH2 + ISOTOPOMERS
c-CH2SCH2
 Some Fractional Abundances in
TMC-1
• CO 1(-4) • OH 2(-7)
• HCN 2(-8) • NH3 2(-8)
• C4H 9(-8) • HC3N 2(-8)
• HCO+ 8(-9) • N2H+ 4(-10)
• c-C3H2 1(-8) • HNC 2(-8)
• HC9N 5(-10) • O2 < 8(-8)
IMR – Ion-Molecule Reactions
Introduction
Energies E/k→T
logTe (K)
experiments 1eV ~ 11 400 K Solar nucleus
1K ~ 9x10-5eV

Plasma in earth’s

100eV 106magnetosphere
K
Ionization

Solar corona
Elekt. excitacion

BEAM, MB 10eV 105 K

Solar wind
near the Earth
blesk
1eV 104 K
Ionosféra
DT, SIFDT
Vibration

0.1eV 1000 K F2 F1

D E Air
FA, SIFT 0.01eV 100 K Afterglow
0 2 4 6
logNe (cm-3)
Rotation

RF-TRAP 1meV 10 K ISM

ATHENA
1
4K
ATRAP 4K
0.1meV 1 K e+, p 0
TRAP
Energies
Physical Chemistry Reaction Kinetics
Rate of Reaction
Consider the homogeneous reaction (occurs entirely in one phase)
aA + bB +  → eE + fF + 

1 dni
v= dn A / dt a
=
1 dn A 1 dnB
 i dt dnB / dt b a dt
=
b dt

The rate of conversion J

1 dn A 1 dnB 1 dnE 1 dnF

J − =− == =
a dt b dt e dt f dt

At equilibrium, J = 0
33
Physical Chemistry Reaction Kinetics
Rate of Reaction
The rate of reaction r

J 1  1 dn A 
r  = − 
V V  a dt 

At constant V

1 d [ A] 1 d [ B] 1 d[ E ] 1 d[ F ]
r=− =− == = =
a dt b dt e dt f dt

mol dm-3 s-1

mol cm-3 s-1
34
Physical Chemistry Reaction Kinetics
Rate Laws
For many reactions

r = k A B L

k: rate constant (rate coefficient), k = f (T, P)

, , : order or partial order

+ +  +  n : overall order

The expression for r as a function of

concentrations at a fixed temperature is
called the rate law.
35
 r = k A B L

[He]_62K = 1.65E13 cm-3

[He]_104K = 2.15E13 cm-3
Physical Chemistry Reaction Kinetics
Reaction Orders
r = ko Zero-order

r = k A First-order

r = k A2 r = k AB Second-order

r = k A B
2 r = k AB2 Third-order

r = k AB−2 Negative First-order

r = k AB1 / 2 1.5-order

(
r = k AB/ 1 − B1 / 2 ) No simple order
38
First-order reaction
A➔B+C

Unimolecular reactions
A+ → product A+ →B +
kUNI = 1 /  UNI
d [ A+ ]
= −kUNI [ A+ ] = −[ A+ ] /  UNI [kUNI ] = s −1
dt

A+ → B+ 2

A
Ion current [au]
product
1

B+ → product
B

0.00 0.01 0.02

Reaction time
A+ → product
+
kUNI = 1 /  UNI
d[ A ]
= −kUNI [ A+ ] = −[ A+ ] /  UNI
dt [kUNI ] = s −1
+ + − kUNI t + −t / UNI
[ A ]t = [ A ]t =0  e = [ A ]t =0  e

A+ → B+
C+
1
A+ → B + → C +
Ion current [au]
2
Ion current [au]

B+
1

0.00 0.01 0.02

Reaction time

0.1 A+
+
B
+
A
0.01
0.00 0.01 0.02
Reaction time
Physical Chemistry Reaction Kinetics

First-Order Reactions
d [ A+ ]
= −kUNI + +
[ A ] = −[ A ] / 
UNI
 A =  Ao e − k At
dt
ln A = ln Ao − k At
A = e− k At
Ao
[A]/[A]o

t ln[A] t
First-order reaction: [A]/[A]o vs t First-order reaction: ln[A] vs t
Unimolecular reactions Reaction rate coefficient
+ +
A → product dA
= −kUNI A+ = − A+ /  UNI
+ + +
dt
A → B →C

C+C +
1
Ion current [au]

Ion current [au]

1 A+
0.1

B+ B
+

+
B
+

+ A
A
0.01
0 0.00 0.01 0.02
0,00 0,01 0,02 Reaction time
Reaction time
Unimolecular reactions Reaction rate coefficient
+ dA+
A → product dt
= −kUNI A+ = − A+ /  UNI

[ A+ ]t = [ A+ ]t =0  e− kUNI t = [ A+ ]t =0  e−t /UNI

+ + +
A → B →C

A+ → B + → C + 1
C
+

Ion current [au]

C+C +
Ion current [au]

1 A+ 0,1

+
B
+
B +
A
B+
+
A
0,01
0
0,00 0,01 0,02 0,00 0,01 0,02
Reaction time
Reaction time
Example Photodissociation

+
H 3 + h → ( H ) → H + H 2 +
+*
3
+ + − kUNI t + − t / UNI
[ A ]t = [ A ]t =0  e = [ A ]t =0  e

D+3
*
+
D3 + h → ( D3 ) → D + + D2
*

H+3
*

Radiative lifetime
excitation +(v)
Radiative decay of H3

H3+(v)

Radiative lifetime
 Reakce II.řádu
2A➔P
A+B➔P
 Binary reactions Reaction rate coefficient
+ +
A + B →C + D [kBIN ] = cm3 s −1

+
d[ A ] +
= −k BIN [ A ][ B ]
dt
Often it is written in simpler form
using A+ instead of [A+]

dA+
= −k BIN A+ B
dt
 Binary reactions Reaction rate coefficient
+ +
A + B →C + D
+
d[ A ] +
= −k BIN [ A ][ B ] For [A+]<<[B]
dt
+ + − k B t
[ A ]t = [ A ]t =0  e
1 +
C

Ion current [au]

0,1

+
B
+
A
0,01
0,00 0,01 0,02
Reaction time
 Binary reactions Reaction rate coefficient
+ +
A + B →C + D dA+
= −k BIN A+ B
+ + − k B t dt
[ A ]t = [ A ]t =0  e
+ + +
A → A1 → A2

Sequence of reactions 1 +

Ion current [au]

A 2
+
A + + B → A1 + C
+ + +
A1 + B → A2 + D 0.1 A1

+
A
0.01
0.00 0.01 0.02
[B]t
 1 +
H 3O
T = 16.1 K H2O+ + H2→ H3O+ + H
0.1
Ni(t )/N(t0)

+
H2O
0.01 H3O
+

 H 2O
+

0.001
10 20 30 40 50 60 70 80
A+ + B → C+ + D
t (ms)
+
dA
= −k BIN A+ B
dt

+ + − k B t
[ A ]t = [ A ]t =0  e
 Sequence of reactions
OH+ + H2→ H2O+ + H
H2O+ + H2→ H3O+ + H
Experiment in 22-pole trap
 T = 44 K
1
+ +
A + B →C + D
+
H 3O
Ni(t )/N(t0)

dA+
= −k BIN A+ B
0.1 +
OH
+
H 2O
+
H2O
H3O
+
dt

+
OH
0.01
0 10 20 30 40 50 60 70 80
t (ms)

[ A+ ]t = [ A+ ]t =0  e − k B t
 O+ + H2→ OH+ + H
OH+ + H2→ H2O+ + H
H2O+ + H2→ H3O+ + H
 T = 39 K
100 +
H3O
H
+ A+ + B → C+ + D
10 H2O
+

dA+
N (t )

+
H
O
+
= −k BIN A+ B
dt
+
OH +
1 H2O
+ OH
+
H3O +
O

0.1
0 20 40 60 80 100
t (ms)

[ A+ ]t = [ A+ ]t =0  e − k B t
Oxygen and its components in
the interstellar medium
O2, P. F. Goldsmith H O
2002

OH+, F. Wyrowski
2010

H2O, A. C. Cheung 1969

H2O+, V. Ossenkopf 2010

H3O+, J. M. Hollis 1986

2012
2016
O+ + H2→ OH+ + H 2015
O+ + H2→ OH+ + H
O+ + D2→ OD+ + D
2018 O + H2→ OH + H
+ +
Oxygen evolution in
interstellar medium
O+ + H2 reaction in 22 pole
ion trap
O+ + H2 reaction in 22 pole
ion trap
• Různé konfigurace pro různé
experimenty
• Chladící hlavy na 22PT a
zdroji H chladí až do 11 K a 7
K
• Ionty se produkují v iontovém
zdroji
• QP hmotnostní filtr vpouští do
pasti jen ionty, které
vybereme
• QP hmotnostní spektrometr a
detektor jednotlivých iontů
2018

2018
O+ + H2 time evolution of components
Without mass filter
N2O in source
10000 + +
O H2O
+ +
N H3O
1000

+ +
O + H2 → OH + H
+
OH
100

counts
10

100 1

0.1
12 13 14 15 16 17 18 19 20 21
mass (a.m.u)

10 With mass filter

Ni

+
O
1000

1
+
+ + H2O
H H2O 100
counts

O
+ + T22PT = 50 K
H3O
+
OH
10
0.1
0 20 40 60 80 100
t, ms 1
14 15 16 17 18 19
mass (a.m.u)
 0
(t) T = 73 K
10

-1
10
N(t)/NO(t0)

-2
10

-3
10

-4
10
0
(t) T = 13 K
10
+
O
+
OH
-1 +
H2O
10
+
N(t)/NO(t0)

H3O
+

-2
10

-3
10

-4
10
0 50 100 150 200 250
2.5
t (ms)
+ 4 +
O ( S) + H2 → OH + H
+
O + H2 Ee= 50 V 2.0
(t)

k (x10 cm s )
T = 51 K
3 -1
0
10
-9
kL
1.5
-1
10
N(t)/NO(t0)

1.0
-2
TDE
10 n SIFDT
+
H2 sv ; TQDO SIFT
H Martinez 2004
 O
+ H2 O
+
0.5
n
sv (GIB) Burley ICR
OH + + H2 GomCar 2014 present exp.
OH H3 O FA
-3
10 TDE present averaged GIB
0 20 40 60 80 100
0.0
t (ms) 10 50 100 1000 7000

T (K)
  T = 39 K
100 +
H3O
+
H
10 H2O
+
N (t )

+
H
+
O
+
OH +
1 H2O
+ OH
+
H3O +
O

0.1
0 20 40 60 80 100
t (ms)

1
 T = 44 K H 3O
+

1 T = 16.1 K
+
H 3O
0.1

Ni(t )/N(t0)
Ni(t )/N(t0)

+
0.1 + H2O
OH
+
H 2O 0.01 +
H2O
+
H3O


+
H3O +
H 2O

OH
+ 0.001
0.01 10 20 30 40 50 60 70 80
0 10 20 30 40 50 60 70 80 t (ms)
t (ms)
 + +
OH + H2 → H2O +H
+ SIFT (Jones, 1981)
Average data starting from O + +
Average data starting from 2OH H O + H → H3O + H
+
2
ICR (Kim,1975)
FA (Fehsenfeld,196
FDT (Dotan, 1980)
maximum error
theory (Martinez, 2015) L H2O
k theory QCT (Song,

kL OH experiment (Martinez, 2015)

theory QD (Song, 2
experiment (Song, 2
SIFT (Jones, 1981)
FA (Fehsenfeld, 1967)
QCT SIFT (Shul, 1988)
1 ICR (Kim, 1975)
1
kOH(10 cm s )

QCT Theory QD Song (2016)

kH O(10 cm s )
3 −1

3 −1
Theory QCT Song (2016)
Average data
maximum erro
Average data
−9

−9
Average data
theory (Shaun
QD QCT VT-SIFT (Sha

2
22PT - O+ SIFTa 22PT - H2O+ SIFT

22PT - OH+
FA max. error ICR QCT
SIFTb FA
max. error ICR
22PT (from O+) FDT QD
Theory QCT Martinez Theory QD Song 22PT (from OH+) theory QCT Song
Theory QCT Song theory QCT Shaun theory QD Song
VT-SIFT
DQDO
VT- SIFT

10 100 1000 10 100 1000

T (K) T (K)

 T = 44 K 1
H 3O
+
1
H 3O
+ T = 16.1 K

0.1

Ni(t )/N(t0)
Ni(t )/N(t0)

0.1 + +
OH
+
H 2O H2O
+
H2O 0.01 H3O
+
+
H3O
 +
H 2O

+
OH 0.001
0.01 10 20 30 40 50 60 70 80
0 10 20 30 40 50 60 70 80
t (ms)
t (ms)
2018
Fig. 4
Fig. 5
Fig. 6
09. 10. 2019, correction for 3% H2
 Binary reactions

+ + dA+
A + B →C + D = −k BIN A+ B
dt
3 −1
[kBIN ] = cm s

+ +
A + B → A1 + C
+
→ A2 + C
Reaction cannels
Branching ratio
 H 2+ + Ar  ArH + + H
Single collision
x
H2 + H
Ar
vr
H2 + ArH+ H 2+
I0 I
Ar s(vr)
vr Ar
ArH+
Ar
Ar Ar Ar (Ar.H2)+
I(x)
H
reaction cross section I=I0exp(-snArx)

dI dI
~ − IN = −sIN Proportionality factor
dx dx

dI
Idx
=
d ln( I )
dx
= −sN I ( x) = I 0 exp( −sNx)
polarizab
Single collision H 2+ + Ar  ArH + + H
x
H2 + H
Ar
vr
H2 + ArH+ H 2+
I0 I
Ar s(vr)
vr Ar
ArH+
Ar
Ar Ar Ar (Ar.H2)+
I(x)
H
reaction cross section I=I0exp(-snArx)

 coll = nVrel = nS = n 2 = nvs = (2r+R)

 coll = nvs Vrel 2

dI I n
=− = − I coll
dt  coll
I (t ) = I 0 exp( − collt ) = I 0 exp( −sn rel t )
 Simple picture of ion – molecule interaction

f=e/r

+
f= -e/2r4
d=e/r2

E(ion) = 2d/r3 = 2e/r5  - polarisability

F(ion) = 2e2/r5 U(pot) = -e2/2r4
Two particles interaction

A+ v0
+
vr r
Q

B
Simple picture + F(r) ~ 2e2/ r5

U(pot) = -e2/2r4
U(kin)=v0/2

For U(pot) > U(kin) we have capture ➔

Capture is for r<r where U(r, pot) = U(r, kin)
➔v02/2 = e2/2r4
➔ s~ r2= {2e2/2 (v02/2)}1/2
➔s~ e/v0 {/}1/2
2e 
Using SI units: s 0 = r =2

v0 (4 0 ) 
0
Ion induced dipole interaction
E = (1 / 2) v02

E = (1 / 2)  (r 2 + r 2 2 ) + V (r )

L = v0b = r 2

E = (1 / 2) r 2 + (1 / 2) r 2 2 + V (r )

U (r ) = (1 / 2) r 2 2 + V (r )

Eb 2
U (r ) = + V (r )
r2
E = (1 / 2) r 2 + U (r )

metastabile orbit

(1 / 2) r 2 = 0  E = U (r0 )

For ion induced dipole force

e 2
r0 = ( )1/ 4

(4 0 ) 2 v02

b0 = 2r0

2e 
s 0 = b02 =
v0 (4 0 ) 
Collisional rate coefficient 2e  1 
s 0 = r02 = ~
v0 (4 0 )  v0 
Exothermic reaction
1
+
H + D2  D2 H + H 2
3
+
s collisional ~
v0

k=  vs (v)dv = k (T )
Max(T )

k(T) reaction rate coefficient

kcoll(T) collision rate coefficient

Collision rate coefficient
2e  1 
s 0 = r02 = ~
v0 (4 0 )  v0 

H 3+ + D2  D2 H + + H 2
o
105 

1
s~
v
1
s~
v

k=  vs (v)dv = k (T )
Max(T )

k(T) reaction rate coefficient

kcoll(T) collision rate coefficient

Collision rate coefficient -Langevin rate coefficient

H 3+ + D2  D2 H + + H 2

1
2e  s~
s 0 = r = 2 v

v0 (4 0 ) 
0

1  v
s coll = s L = const ~ s 0 0 cm 2
v  v

v0
kcoll (T ) =  sv  ~  s 0 v ~ const H ~0.666793
v He ~0.204956
 −9 
Li ~24.3
kcoll = kcoll = const ~ 3.34 x10 cm3 s −1 ; C ~1.76
  Ar ~1.64
 in Debye CO ~1.95
 in atomic units H2 ~0.8
C2H4 ~4.5
Ind. dipole d=e/r2➔[=dr2/e]=err2/e]=r3]
~dr2/e→if r~A and d~eA→ ~A3 kL~10-9cm3s-1
 +
Cross section of IMR H3 + D2 → D2 H + + H2

s~()−05~1/v

1  v
s coll = s L = const ~ s 0 0 cm 2
v  v
 +
Cross section IMR D3 + H 2 → H 2 D+ + D2

Endothermic reaction
Cross section IMR He + + O2 → O + + O + He

s~()−05~1/v
Hard core cross section
s~ s0
Decay of plasma – change of plasma composition
H3+ → H3O+
H3+ + H2O → H3O+ + H2
Ion density in low temperature plasma, e.g. DC discharge [H3+]~1010cm-3
“Pure He” … grade 5 …. 99.999% ….0.001 % of impurities
Water impurities ~10-5 Torr ➔3x1011cm-3

dH 3+
= −k[ H 3+ ].[H 2 O] = −[ H 3+ ] /  H 2O
dt
[ H 3+ ] = [ H 3+ ]0 . exp( −k[ H 2 O]t ) = [ H 3+ ]0 . exp( −t /  H 2O )
1 1
= ~ ~ 0.0017 s ~ 1.7 ms
k[ H 2 O] (2.10 −9 ) x(3.1011 )
Collision rate coefficient
Ion-molecule -Langevin rate coefficient
interaction v0
+
1 e r
 (r ) = A+ vr
4 0 r
Q
B
r
+ U ( pot ) = −
 e2
 e
 (r = 0) = −
4 0 2r 4  4 0 2r 4
  e r
d=
4 0 r 2 r
pro U(pot) < U(kin) je záchyt ➔ v 2  e2
=
0

 - polarizability Záchyt pro r<r kde U(r, pot) = U(r, kin)

2 4 0 2r 4

2e 
Collision cross section of IMR s = r 0 = 2

Langevin cross section of IMR v0 4 0 

kcoll(T) collision rate coefficient
1  1
Langevin rate coefficient s = r 0 ~ ~ 2

v0  
Collision cross section of IMR +
v0
1 e r
 (r ) = A+ vr
4 0 r
Q
B
r
+ U ( pot ) = −
 e2
 e
 (r = 0) = −
4 0 2r 4  4 0 2r 4
  e r
d=
4 0 r 2 r
pro U(pot) < U(kin) je záchyt ➔ v 2  e2
=
0

 - polarizovatelnost Záchyt pro r<r kde U(r, pot) = U(r, kin)

2 4 0 2r 4

2e  H 3+ + D2  D2 H + + H 2
s = r = 2

v0 (4 0 )  100
0

10
1  1 2 Neutrals
s = r ~ ~ 2
1Å
v0  
0
H
20K 300K

 km
Reaction Rate of IMR relevant for ionosphere
400 He+
H+ Inosféra
kcoll ~10-9cm3s-1
kIMR 300 N+ O+

F2-max.

He+ + N2
200 O2+ NO+
N+ + O2 1975-90 F-region
+
O2 + NO
O+
+
N2+
N

n+
E-region
100
n-
90

N2+ + O2 80 NO+ electron-ion D-region

1990-00 70
higher
plasma

ion-ion
1 order plasma
+ 3 2 clusters
60 H3O
O+ + O2 H3O+.(H2O)
50 n
101 102 103 104 105 106 cm-
3

O+ + N2
IMR thermal
Ionic composition of the atmosphere
The ion chemistry of the lower atmosphere

Binary reactions

Ternary reactions
Branching ratio of IMR k1
2
+
AB + C  ( A.BC + ) # ⎯⎯→ AB + C +
 −1
3
⎯⎯→ AC + B +
4
⎯⎯→ AC + + B
 products
E0
reactants

Reaction coordinate
Reaction coordinate

  
D
D D

Reaction coordinate Reaction coordinate

Reaction coordinate

Endothermic Exothermic

D

Reaction coordinate

s
D ……. EA ~D

Reaction coordinate
Collisional Energy
Collisional Energy EA
Kinetics of elementary process

k=  f (v ).v.s (v )dv = k (T )
Max ( T )

~Nvs
~1/Nk
s

Eel
Ea Collisional Energy
s

Collisional Energy
Ea
Excitation energies
s

Collisional Energy
E0
D ……. EA ….activation energy Ea
s

Collisional Energy
E0
Arrhenius plot
Energies of H2 and D2 H2 Be=60.80 B
250

1eV corresponds to ~ 11604K D2 Be=30.429

200 H2
HD Be=45.655

meV
150

j E/meV E/in K 300K 250K 80K 35K low

100
H2 0 0 0 0.128 0.150 0.248 0.25 1/4

energy
D2
1 14.7 170.6 0.657 0.694 0.75 0.75 3/4 50

2 44 510.6 0.117 0.098 0.002 0

0
3 87 1009.5 0.092 0.055 0 0 0 1 2 3 4 5

4 145 1682.6 0.004 0.0016 0 0 j

5 215 2494.9 0.001 0.0002 0 0

D2 0 0 0 0.179 0.213 0.552 0.664 2/3
1 7.3 84.71 0.202 0.227 0.329 0.333 1/3
50

2 22 255.29 0.383 0.384 0.114 0.002 H2

3 44 510.6 0.115 0.098 0.004 0 40

meV
4 72 835.5 0.098 0.066 0.0001 0 HD
30

5 108 1253.2 0.015 0.008 0 0

20

D2

energy
HD 0 0 0 1 10

1 11.04 128.1
0
2 33.05 383.4 0 1 2

H2 and D2 are taken from O. Wick dissertation

HD is calculated using Be from Herzberg and comparison with H2 from table
1eV corresponds to ~ 11604K

D

Reaction coordinate
Chemická rovnováha je takový stav soustavy, v němž se
z makroskopického hlediska nemění její složení, i když v ní neustále
probíhají chemické děje.

Obr. 22-1: Příklad časových změn skutečné okamžité látkové koncentrace látek
pro vratnou reakci
IMR N 4+ + He → N 2+ + N2 + He
Energy dependence
Endothermic IMR
COLLISION INDUCED DISSOCIATION
-10
10

-11
10

s()
k2 [cm /s]

-12
10
3

+
CH3O
-13 +
10 N4
+

Ea  (CO)2
+
-14
10 CH5
+
C2H5
-15
10
1

Eb [eV]
CID – binary process
+
CO  N 2 + N2 ⎯⎯→
⎯ kCID
product
+ +
CO .N2+N2 ---> CO +N2+N2
1E-12

kf (cm s )
3 -1
1E-13

0,05 0,1 0,15

KECM (eV)

Association reactions - three body reactions

+
CO + N2 + N2 ⎯⎯⎯→ CO +  N 2
k ASOC
+ N2

kf
CO +  N 2 + N2 ⎯⎯⎯→
⎯⎯
⎯ CO + + N2 + N2
kr
IMR k = k(1/E) diagram
-10
10
COLLISION INDUCED DISSOCIATION

-11
10

-12
10
k2 [cm /s]

+
3

CH3O
-13 +
10 N4
+
(CO)2
+
-14
CH5
10 +
C2H5
-10
ARRHENIUS PLOT
-15
10
10
0,1 1 +
CH3O
Eb [eV] +
-11 N4
10 +
(CO)2
+
CH5
-12
10 +

k2 [cm /s]
C2H5

f () s()

3
-13
10

T -14
10

Ea  -15
10
0 1 2 3 4 5 6 7 8 9 10

1/Eb [1/eV]
The Arrhenius Equation
Experimental observation : k=Aexp(-B/T)
1889 Arrhenius sugested expression:
k=Aexp(-Ea/RT) Arrhenius equation
A - pre exponential factor or Frequency factor
Ea – activation energy

Better definition is lnk = (-Ea/RT) +lnA

Dependence of lnk versus 1/T will have a slope equal -Ea/R

Boltzmann’s Distribution Law -10

10
ARRHENIUS PLOT
Boltzmann distribution law -11
CH3O
N4
+
+

10

Ni/N = [exp(-i /kT)]/[ exp(-i /kT)] (CO)2

+
+

-12 CH5

k2 [cm /s]
10
+
C2H5

3
N2/N1 = exp(-(2−1)/kT) -13
10

-14
10

Ni/N = gi [exp(-i /kT)]/g -15

10
0 1 2 3 4 5 6 7 8 9 10

g – molecular partition function 1/Eb [1/eV]

Endothermic reactions f () s()

Fraction of collisions, f(), with energy  T

f() = dN()/N= exp(-  /kT)d /kT
Fraction of molecules with energy >  is : Ea 

  1
F =  f ( ' )d ' =  exp(- ' /kT)d ' =exp(-/kT) = exp(- E/RT)
kT
 E
A + B → products
dNA/dt= -kNANB

dNA/dt=ZABexp(-E/RT) = NANBs<ur> exp(-E/RT)

k= s<ur> exp(-E/RT)

From experiment
k=Aexp(-Ea/RT)
Potential energy surface 3D

XY + Z → ZY + X
Reaction coordinate
Temperature dependence of IMR - CID
COLLISION INDUCED DISSOCIATION
AB + + M ⎯
⎯→
k
A+ + B + M
CID - can be considered as binary process
+ +
N 4 + He → N 2 + N2 + He
-10
10

Bond energy ~1eV

+
N4
400K
ARRHENIUS PLOT +
-20 (CO)2 calc.
10 300K +
N4 calc.
+
-30 200K (CO)2
10
+
+]= [N4+]0exp(-EA/kT)

k2 [cm /s]
[N4 10
-40 N4

3
-50 100K
10 +
(CO)2
120K
-60
10 80K

Can be considered also as unimolecular decay !!! 10

-70

-80
10
+ +
N →N +
0 20 40 60 80 100

4 2 N2 1/Eb [1/eV]

J. Glosik, V. Skalsky and W. Lindinger,

Observation of Arrhenius behaviour over 56 decades: Dissociation of N4+ Ions, Int. J. Mass .Spectr. Ion Proc., 134, 67, 1994
J. Glosik, V. Skalsky, C. Praxmarer, D. Smith, W. Freysinger and W. Lindinger,
Dissociation of Kr2+, N2Ar+, (CO)2+, CH5+ and C2H5+ Ions Drifting in He, J. Chem. Phys., 101, 3792, 1994
IMR thermal
-10
10 +
N4
400K
ARRHENIUS PLOT +
-20 (CO)2 calc.
10 300K +
N4 calc.
+
-30 200K (CO)2
10
+

k2 [cm /s]
-40 N4
10

3
-50 100K
10 +
(CO)2
120K
-60
10 80K

-70
10

-80
10
0 20 40 60 80 100

1/Eb [1/eV]

[N4+]= [N4+]0exp(-EA/kT)
IMR Energy dependence eV region
Endothermic IMR
N 4+ + He → N 2+ + N2 + He

COLLISION INDUCED DISSOCIATION

-10
10

-11
10

-12
k2 [cm /s] 10
3

+
CH3O
-13 +
10 N4
+
(CO)2
+
-14
CH5
10 +
C2 H5

-15
10
0,1 1

Eb [eV] ~T

At this point without discussion

Reaction rate coefficients
Typical values of at 300K (approximate values)
• reactants products rate coefficient
•
Electron atomic ion rec. A+ + e- ➔ A + h ~10-11cm3s-1
•
Electron - ion recomb. O2+ + e- ➔ O+O 2x10-7cm3s-1
• Electron – cluster ion recomb. H5+ + e- ➔ products 3.5x10-6cm3s-1
• Ion – ion recombination Ar+ + Cl- ➔ Ar + Cl 2x10-8cm3s-1
• Ion – molecule reactions H2+ + H2, ➔ H3+ + H 2x10-9cm3s-1
H3+ + H2 + He ➔ H5+ + He keff BIN= k3x[He]
k3<2x10-29cm6s-1
• Attachment CCl4 + e- Cl- +CCl3 ~10-7cm3s-1
• Penning ionization He* + Ar Ar+ + e- + He 7x10-11c .
 Rate coefficients

A+ 3 -1
B products % k[cm s ] T
 Importance of Ion-Molecule Reactions
Products

EA
Reactants

Arrhenius:
k(T) = <sv> = A exp (-EA/kT)

Neutral-Neutral Reactions
A  10-11 cm3/s
EA  2000 K
TMC = 10 K

Ion-Molecule Reactions
10-7 cm3/s > A > 10-9 cm3/s
EA  0 K

Cosmic Ray Ion-Molecule

Recombination
Ionization Reactions
E. Herbst, The Physics and Chemistry of Interstellar MCs (1993)
 Details of Potential Energy Surface

Transition
E
State

Reactants kT

Products
Association

Rotational Energy, Zero Point Energy and Fine Structure Energy

 Example I:
Negative Temperature
Dependence

NH3+ + H2 → NH4+ + H

Gas Phase Formation of Ammonia

NHn+ + H2 → NHn+1+ + H

n = 0,1,2,3
Implications of a barrier along reaction path
Products

EA
Reactants

Arrhenius:
k(T) = <sv> = A exp (-EA/kT)

T/K
10 100 1000
Negative Temperature Dependence
NH3+ + H2 → NH4+ + H

Experiment

Theoretical
Prediction

Herbst et al. J.Chem.Phys. 1991

 Lowest energy path for
NH3+ + H2 → NH4+ + H

kcal/mol

van der Waals binding

Herbst et al. J.Chem.Phys. 1991

 Negative Temperature Dependence
NH3+ + H2 → NH4+ + H

l k << kL 1 in 10000 collisions leads to reaction

l Turnover at 100 K

l barrier height 4.8 kcal/mol (2400 K)

l Tunneling is a dominant mechanism

at low temperatures
Ion molecule reactions
Reaction coordinate
Závislost reakční rychlosti na teplotě
Reaction mechanism
Reaction coordinate


Potential energy 3D
Reaction proceeding via intermediate states
 Rate Law
• rate = k[A]x[B]y
• rate order = x + y
• knowledge of order can help control reaction
• rate must be experimentally determined

Injection

Flow meter

mixing
detector
FA– Flowing Afterglow principle

Reactor with plasma

Techniques for study of IMR – FALP
1965
Experimental studies of IMR ➔FA

Flow ION DETECTOR

PLASMA Tube
SOURCE
PUMPING
REACTANT GAS

Diameter ~7cm; Length 100cm, Gas Velocity 100m/s,

Pressure ~1Torr, Plasma Density ~ne=n+~ 1010cm-3
Techniques for study of IMR
Techniques for study of IMR – reality
Techniques for study of IMR – reality
Techniques for study of IMR – reality
Techniques for study of IMR
FA– Flowing Afterglow +
H + CO  HCO + H +
3
100-700 K
He+ H2 CO H2
H3+ COH+
Hem HCO+ HCO+
e-
He2+

microwave CO
H2
discharge

He
He REACTION QMS

nH3+. =(nH3+). 0 exp(-knArt)

n/exp(t/)

+ +
Ar
He
He2
+
H3
+ t=L/v
t
L
Formation region Reaction region
FA– Flowing Afterglow +
H + CO  HCO + H +
3
100-700 K
He+ H2 CO H2
H3+ COH+
Hem HCO+ HCO+
e-
He2+

microwave CO
H2
discharge

He
He REACTION QMS

0
H2 CO

He w
FA– Flowing Afterglow 2005
MFF.CUNI.CZ
FA– Flowing Afterglow 2005
MFF.CUNI.CZ
FA– Flowing Afterglow 1965 -2006
MFF.CUNI.CZ

CU – Chemistry 1980:
Eldon Ferguson watching the flow-tube centers
FALP – MFF.CUNI.CZ FA 2002
0
Ar H2

Plasma, IMR, Recombination

Diagnostics
He w

2002

2004

2005
O.Novotný
microwave discharge Principle of Flowing Afterglow Langmuir Probe - FALP

Formation of H3+ in He/Ar/H2 mixture (10 Torr)

He+
Ar H2 H2
Hem Ar+
e-
ArH+, H2+ H3+ + e-
He2+
H2

Ar H2 H5+ + e-

He
He RECOMBINATION

Te ~2eV Te= Ti =TG = 170 - 260K

Apparatus -FALP

MW Ar H2
discharge

He
discharge Ar H2

-
10 e

Kinetics 10
[H2] = 5x10
12
cm
-3
He
He
He2
+

+
+ -7 3 -1
(H3 ) = 2x10 cm s +
9 Ar
n [cm ]

10
-3

+
Ar2
+
ArH
+
H2
8 +
10 H3
+
H5

-10 0 10 20 30
t [ms]

α ~ 5x10-9 cm3s-1
Plasma decay can be monitored up to 35 cm ➔ 65 ms, Temperature – 130 - 300 K Pressure up to 12 Torr
Evolution along the flow tube
+ + − DL / 2v
[ A ] L = [ A ] L =0  e
+ + − const1 . D0 p0 L / Q + − const2 . L / Q
[ A ]L = [ A ]L=0  e = [ A ]L=0  e
Reactant Port
17
10 p = 9,5Torr
-1
v = 85ms
16
10
koncentrace [m ]
-3

15 e
10
*
He
+
14
He
10 +
He2
+
Ar
13 +
10 Ar2
+
O2
+
12
10 O4
-20 -10 0 10 20

L [cm]
Ion-molecule reactions
 Flowing Afterglow 1968
microwave discharge

Ar Reactant

He
He He+ Ar+ Afterglow

Te ~2eV Te= Ti =TG = 170 - 260K

Selected Ion Flow Tube - SIFT
Ion-molecule reactions
Diffusion and reaction + + − k B L / v − constL/ Q
[ A ]t = [ A ]t =0  e e
Measurements by mass spectrometer vat fixed position
H 3O + + CH 3COCH 3 → CH 3COCH 3 H + + H 2O

1
+

Ion current [au]

H ·(CH3COCH3)2

0,1

+
CH3COCH3H
+
H3O
0,01
0,00 0,01 0,02
Flow of Acetone [sccm]
IMR thermal
 + + − k B L / v − constL/ Q
IMR C60+ [ A ]t = [ A ]t =0  e e
IMR – SIFT → Proton Transfer Mass Spectrometry
Spanel, Smith [ A+ ] = [ A+ ]  e− k B L / v e−constL/ Q
t t =0

Primary ions
H3O+, O2+, NO+
+
H 3O + + Cn H m → Cn H m+1 + H 2O
Selected Ion Flow Tube - SIFT
 + +
SIFDT N4 + He → N 2 + N2 + He
100 K – 3eV
Ion Source He, N2
N4+ N2+
With QMS N4+ QMS

He N2

Ion Source N2+

N4 +
N4+
QMS
With QMS


E
 SIFDT experiment
Selected Ion Flow Drift Tube – SIFDT
vd ´=   E 0 =  
p 273

760 T

3 v d2
KEion = k bTg + (mc + mi )
2 2
3 1 m + mc
KE r = k bTg + mr vd2 ( i )
2 2 mi + mr

3 1
KEc = k bTg + mc vd2
2 2
Proton transfer mass spectroscopy - Innsbruck

+
H 3O + + C6 H 6 → C6 H 7 + H 2O
 SIFDT time of flight
100
+
CO .N2 Time of flight“ spektrum iontů N4+ a
80
CO+.N2 v dusíku a průběhy odpovídajících
60
N4
+
pohyblivostí.
counts [au]

40

20

0
100 200 300 400 500 600

time [au]

2,8
2,6
2,4
2,2
2,0

µ 0 ( cm s V )
-1
-1 1,8

1,6
2

1,4
+
1,2 CO
+ + +
CO .N2 Mobilities of CO and CO .N2
1,0 +
N4 in N2 buffer
0,8 N2
+

0,6
20 40 60 80 100 120 140 160 180

E/N (Td)
Ion mobilities
Fig. 2

24

22
Mobility of ion SH+ in He
20
K0 [cm2V-1s-1]

18

16

14
0.16 Torr
12 0.22 Torr

10
0 20 40 60 80 100 120 140 21
E/N [Td] 20 +
Reduced mobility of C2H3
19
in He with 1% of H2
18

µ0 [cm V s ]
-1
17

-1
16

2
15
14 0.16 Torr
0.20 Torr
13
0.27 Torr
12 0.31 Torr
11

10
0 20 40 60 80 100 120 140 160

E/N [Td]
Reaction of Si+ ions
+
Si + + C6 H 6 → SiC6 H 5 + H
→ SiC6 H 6+
1,0 +
kCL + Si + C6H6
Si + C6H6
0,8

Product distribution
-9
10
keff [cm s ]

0,6 , 0.14 Torr

3 -1

0.16 Torr
0.12 Torr , 0.22 Torr
0.34 Torr , 0.42 Torr
0.22 Torr 0,4 , 0.30 Torr
0.14 Torr SIFT
0.42 Torr
0.30 Torr 0,2
SIFT

-10
10 0,0
0,1 1 0,1 1

KECM [eV] KECM [eV]

 +
Si + + C6 H 6 → SiC6 H 5 + H
Reaction of Si+ ions
→ SiC6 H 6+
1,0 +
kCL +
Si + C6H6 Si + C6H6

0,8

Product distribution
-9
10
keff [cm s ]
3 -1

0.16 Torr 0,6 , 0.14 Torr

0.12 Torr , 0.22 Torr
0.34 Torr , 0.42 Torr
0.22 Torr 0,4 , 0.30 Torr
0.14 Torr SIFT
0.42 Torr
0.30 Torr
0,2
SIFT

-10
10 0,0
0,1 1 0,1 1
KECM [eV] KECM [eV]

kCL +
Si +C6H6
-9
k [cm s ] 10
3 -1

-10
10


, 0.30 Torr , 0.42 Torr

, 0.14 Torr , 0.22 Torr
-11
10
0,1 1

KECM [eV]
Kinetic energy dependence of IMR 1000K 10 000K

kL +
Si + C2H6
eV range 10
-9

k [cm s ]
3 -1
Si + + C2 H 6 → SiCH 3+ + CH 3 0.19 Torr
0.28 Torr
→ SiC2 H 4+ + H2 0.16 Torr
SIFT

→ SiC2 H 5+ + H 10
-10

0,1 1
+
→ SiC2 H 6 KECM [eV]

1,0
+
0,9 Si + C2H6

Product distribution
0,8

0,7
+
0,6
SiCH3
+
0,5 SiC2H4
+
0,4
SiC2H5
0,3 +
SiC2H6
0,2

0,1

0,0
0,1 1

ECM [eV]

J. Glosík, P. Zakouril, W. Lindinger,

Experimental study of the reactions of Si+(2P) ions with several small organic molecules at near thermal energies,
Czech. J. Physics, 47 (1998), pp. 29-44
SIFDT
3 v d2
10
-10
ARRHENIUS PLOT KEion = k bTg + (mc + mi )
10
-15
N4
+

400K
2 2
-20
10 +
CH5 300K

-25
10
k2 [cm /s]

-30
10
+ +
3

N4 C2H5
-35
10 +
N4 calc.
+
-40
N4 equil.
10 CH5
+

+
-45 CH5 calc.
10 + H2COH
+
C2H5
+
-50 C2H5 calc.
10 +
H2COH
+
10
-55 H2COH calc.

0 10 20 30

1/Eb [1/eV]

E
Fig. 1

[He] = 2.39E13 cm-3

Fig. 2

[He]_62K = 1.65E13 cm-3

[He]_104K = 2.15E13 cm-3
Fig. 3
Fig. 4
Fig. 6
Fig. 7
09. 10. 2019, correction for 3% H2
Fig. 8
 Reakce II.řádu
2A➔P
cA 
dc A
−  2 = k  dt
cA0
cA 0 poločas reakce:
cA
c  −1
−   = k
A

 − 1  cA0 cA =
c A0
2
1 1 1 2 1 
− = k  0,5 =  −  =
1
c A c A0 k  c A0 c A0  k .c A0
c A0
cA =
1 + c A0 k
Physical Chemistry Reaction Kinetics
Second-Order Reactions
1 1
− = k At
A Ao (17.16)

1 1 {[A]-1}
= + k At
A Ao

{t}
1
t1 / 2 =
[ A]o k A Second-order reaction: 1/[A] vs t
181
VT - AISA 2 Torr of He/Ar/H2
AISA
 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]

processes at high densities at low T

 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]

processes at high densities at low T

 1 exp (t ) − 1 1
Diffusion and recombination dne = − ne2 − D2a ne =α + exp (t )
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)
 e- H + SA
3
Ar+
He+
FORMATION RECOMBINATION

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

11
10
+

10
10
H3+/e- plasma in He/Ar/H2 gas mixture
9
10
0.0 500.0µ 1.0m
dne ne
t [s]
= − eff ne −
2

L
4
dt
1/[H3 ] [10 cm ]
3

3
-11

2
1 1
= + efft
+

[ne ] [ne 0 ]
 eff
0
0.00 100.00µ 200.00µ
t [s]

effective (apparent) binary recombination rate coefficient

Experiments - FALP
 … One remaining
Emotional history of H3+ recombination problem is to understand
the recombination of H3+

H 3+ + e−  H + H 2 , 3H (T=300 K)

A
+
D3 H3
+
SA H 3+
FALP

+
-6 A - M.A. Biondi
=25(−) 1

3
10 MB

+
B - K.B. Persson

+ FALP - H
Stor. Ring
[cm s ]

C - J.A. Mac Donald

3 -1

IR-CRDS
Plasma in TDE
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) - =0
10 G (1)
- >0

1970 1975 1980 1985 1990 1995 2000 2005

1912 … 1936 … 1949 … 1990 … 2003 …2008 …2011…

Storage rings - state selected data:

Doubts 2011 H3+
“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 on its way
Quo vadis
Stationary afterglow + Spectroscopic identification of recombining ions
SA-CRDS
He/Ar/H2

14 0 1 0 1
0 1
0v2 (3,3) 3v2 (4,3) 0v2 (1,1) 3v2 (2,1) 0v2 (1,0) 3v2 (2,0)
12
10 140 ± 10 K

absorption (a.u.)
8
6
4
2
0
-0.1 0 -0.1 0 -0.1 0 0.1
-1
 (cm )

Wavenumber [cm-1] Spin Transition

7234,957 o 0v20(3,3) → 3v21(4,3)
+
d [H ]
= −eff [ H 3+ ]ne = −eff [ H 3+ ]2
3 7237,285 p 0v20(1,1) → 3v21(2,1)

dt 7241,245 o 0v20(1,0) → 3v21(2,0)

All experiments
Physical Chemistry Reaction Kinetics
Third-Order Reactions
d A d A d A d A
= −ak A
3
= −ak A B
2
= −ak AB
2 = −ak ABC 
dt dt dt dt

(Problems 17.17 and 17.24)

d A 1 1
= −k Adt − = 2k At
A3 A 2
 
A o2

Ao
A =
(1 + 2ktAo )
2 1/ 2 (17.24)

189
 Reakce II.řádu
A+B➔P
y…………….zreagované množství

c A = c A0 − y
cB = cB 0 − y
dc A dy
− =
dt dt
1 c B 0 (c A 0 − y )
. ln = k
c A0 − cB 0 c A 0 (c B 0 − y )
Závislost reakční rychlosti na
teplotě
 E/k→T
1eV ~ 11 400 K
logTe (K)Solar nucleus
1K ~ 9x10-5eV

Solar wind
near the Earth
6
100eV 10 K Solar corona

10eV 105 KPlasma in earth’s

magnetosphere
blesk
1eV 104 K
Ionosféra

0.1eV 1000 K F2 F1

D E Air
0.01eV 100 K Afterglow
0 2 4 6

1meV 10 K ISM logNe (cm-3)

ATHENA
1
4K
ATRAP 4K
0.1meV 1 K e+, p 0
Temperature scale should be logarithmic

T
 km
Reaction Rate of IMR relevant for ionosphere
400 He+
H+ Inosféra
kcoll ~10-9cm3s-1
kIMR 300 N+ O+

F2-max.

He+ + N2
200 O2+ NO+
N+ + O2 1975-90 F-region
+
O2 + NO
O+
+
N2+
N

n+
E-region
100
n-
90

N2+ + O2 80 NO+ electron-ion D-region

1990-00 70
higher
plasma

ion-ion
1 order plasma
+ 3 2 clusters
60 H3O
O+ + O2 H3O+.(H2O)
50 n
101 102 103 104 105 106 cm-
3

O+ + N2
 Závislost reakční rychlosti na
teplotě
Arrheniův vztah
Ea
−
k = A.e RT

Ea
ln k = ln A −
RT
A……………frekvenční faktor
Ea…………..aktivační energie
T……………teplota
Závislost reakční rychlosti na
teplotě

DETAIL

reactants products

–
OD (JOD–)+ H2 (JH2)

JOD-
–
OH (0)+ HD(0)
JOD- 3
–
OH + HD
4
2
10 meV TS
0.12 eV TS
1
3 0 0.2 eV –
JH2= 1 – OH (HD)
OD (H2)
2 ortho-H2 25 meV –
H (DOH)
1
0
JH2= 0
para-H2
Dissociative Recombination of
Molecular Ions
Mats Larsson, Ann E. Orel

Cambridge University Press 2008

 Simultánní reakce
Vratné A  B

Paralelní A→B
A→C

Následné A→B →C
 Vratné reakce
k+

A  B
v+ = k + A k-

v− = k − B 
rovnováha.............v+ = v−
k + A = k − B 
k + B r
= =K
k − Ar K…..rovnovážná konstanta
 Paralelní reakce
k1 k2

A➔B A ➔C

Jsou-li obě reakce I. Řádu, pak platí:

v1 = k1 A
v2 = k 2 A
v = v1 + v2
v = (k1 + k 2 )A
 Následné reakce
k1 k2

A ➔ B ➔ C
d A
− = k1 A
dt
d B 
= (k1 − k 2 )B 
dt
d C 
= k 2 B 
dt
řetězové reakce = zvláštní typ následných reakcí
 Chemická rovnováha
k1

A+B  P+Q
k-1

K=
P r Q r
Ar Br
k1
K= Guldberg-Waagův zákon
k −1
 Vyjadřování rovnovážné
konstanty

Předpokládáme reakci:
bB+cC➔xX+yY
Stechiometrické koeficienty – obecně i :
B = -b C = -c X = x Y = y
Rovnici můžeme přepsat do tvaru:
0 = x X + y Y- b B - c C
 Vyjadřování rovnovážné
konstanty
Plynná reakční směs:
DGr0 …..standardní reakční Gibbsova energie
(počítá se pomocí chemických potenciálů)
DGr0 = − RT ln K p
 p x  p  y 
  X0   Y0  
 p X pY 
( )0  i
x y
Kp =   p  p  
= b c  . p i
 
b
 
c 
p
 B   C   p  p B pC  rovn
 0   0 
  p   p   rovn
 Ovlivňování chemických
rovnováh
Henri Le Chatelier
Každá změna vnějších podmínek (akce) vyvolá
v rovnovážné reakční směsi takové děje (reakce),
které ve svých důsledcích působí proti zásahu
zvenčí (akci), jímž byla chemická rovnováha
narušena
 Vliv tlaku na chemickou
rovnováhu
• při reakcích v plynných směsích
• při reakcích, při kterých dochází ke změně
molového čísla

Platí, že zvýšení tlaku (akce), vyvolá děje (reakce)

vedoucí ke snížení tlaku v reakční směsi
 Ternary processes

A+ + B + M → C + + D + M
Association reaction

A+ + B + M → AB + + M
Physical Chemistry Reaction Kinetics
Third-Order Reactions
d A d A d A d A
= −ak A
3
= −ak A B
2
= −ak AB
2 = −ak ABC 
dt dt dt dt

(Problems 17.17 and 17.24)

d A 1 1
= −k Adt − = 2k At
A3 A 2
 
A o2

Ao
A =
(1 + 2ktAo )
2 1/ 2 (17.24)

208
Deuteration is easy
+ +
D3 + D2 + D2 → D5 + D2

+ +
D5 + D2 + D2 → D7 + D2

2000
438
1800 D7 D9 20 s
D5
1600

1400

1200

1000
Counts per filling

800

600

400
D3 D11
200

0,0 2,0 4,0 6,0 8,0 10,0 12,0 14,0 16,0 18,0 20,0 22,0 24,0 26,0 28,0
Mass
Deuteration was not so easy

2000
436-440
D7
1800 D9
1600
D5 1s
2s
5s
1400
10 s
1200 20 s
Counts per filling

1000

800 D11
D13
600

400
D15
D3
200 D17

5,0 10,0 15,0 20,0 25,0 30,0 35,0 40,0

Mass
Association reactions
 Rate Law
• rate = k[A]x[B]y
• rate order = x + y
• knowledge of order can help control reaction
• rate must be experimentally determined

Injection

Flow meter

mixing
detector
Classification of collisions
Classification of collisions
Dynamic of IMR +
N + N 2 → products

Before collision Collisional complex After collision

v1
v0
N+ + N2+
N2 N
N
N N
v2

N + + N2  ( N3 )*+ +
→ N2 + N

2e 
s coll = r =
2

v0 (4 0 ) 
0
Dynamic of IMR N + + N2  ( N3 )*+ → N 2+ + N

Collisional complex After collision

v1

+ N2+
N
N
v2 N
N
Dynamic of IMR N + + N2  ( N3 )*+ → N 2+ + N

v1 Collisional complex After collision

N2+ + N
N v2
N
N
Dynamic of IMR N + + N2  ( N3 )*+ → N 2+ + N

Collisional complex After collision

+
N
N
N
Koniec rosprávky 21 10 2019
Single collision H 2+ + Ar  ArH + + H
x
H2 + H
Ar
vr
H2 + ArH+ H2+
I0 I
Ar s(vr)
vr Ar
ArH+
Ar
Ar Ar Ar (Ar.H2)+
I(x)
H
reaction cross section I=I0exp(-snArx)
 H 2+ + Ar  ArH + + H
Single collision
x
H2 + H
Ar
vr
H2 + ArH+ H 2+
I0 I
Ar s(vr)
vr Ar
ArH+
Ar
Ar Ar Ar (Ar.H2)+
I(x)
H
reaction cross section I=I0exp(-snArx)

dI dI
~ − IN = −sIN Proportionality factor
dx dx

dI
Idx
=
d ln( I )
dx
= −sN I ( x) = I 0 exp( −sNx)
polarizab
Single collision H 2+ + Ar  ArH + + H
x
H2 + H
Ar
vr
H2 + ArH+ H 2+
I0 I
Ar s(vr)
vr Ar
ArH+
Ar
Ar Ar Ar (Ar.H2)+
I(x)
H
reaction cross section I=I0exp(-snArx)

 coll = −nVrel = −nS = −n 2 = −nvs

= (2r+R)
dI I
=− = − I coll
dt  coll Vrel 2
n

I (t ) = I 0 exp( − collt ) = I 0 exp( −sn rel t ) I=I0exp(-snArx)

Collision frequency

1/=kBIN[B]= … nvr ... =[B]vr ….[B] <vr>

kBIN= <vr>
 coll = −nVrel = −nS = −n 2 = −nvs
= (2r+R)
dI I
=− = − I coll
dt  coll Vrel 2
n

I (t ) = I 0 exp( − collt ) = I 0 exp( −sn rel t ) I=I0exp(-snArx)

 H 2+ + Ar  ArH + + H
H2 +

H2 + ArH+
Single collision s(vr)
vr
Ar Ar Ar (Ar.H2)+

k(T)=<vs>
H
reaction cross section I=I0exp(-snArx)
Multiple collision T22PT = 14 K
@T H2
+

H2+ ArH
+

T ion density
100

T  ~ 35 ms

Ar  ~ 1.5 ms
H2+
ArH+
H2+ Pulse ON (+150/-100V)
k(T)
10
-2 -2 -2 -2 -2 -2
0
reaction rate coefficient 1x10 2x10 3x10 4x10 5x10 6x10

time (s)

d(nH2+)/dt=-k nH2+. nAr nH2+. =(nH2+). 0 exp(-knArt)

 +
Collision Cross section of IMR D3 + H 2 → H 2 D+ + D2

Endothermic reaction

Reactive Cross section of IMR

Collision rate coefficient
2e  1 
s 0 = r02 = ~
v0 (4 0 )  v0 

H 3+ + D2  D2 H + + H 2
o
105 

1
s~
v
1
s~
v

k=  vs (v)dv = k (T )
Max(T )

k(T) reaction rate coefficient

kcoll(T) collision rate coefficient

Reaction rate coefficients
Typical values of at 300K (approximate values)
• reactants products rate coefficient
•
Electron atomic ion rec. A+ + e- ➔ A + h ~10-11cm3s-1
•
Electron - ion recomb. O2+ + e- ➔ O+O 2x10-7cm3s-1
• Electron – cluster ion recomb. H5+ + e- ➔ products 3.5x10-6cm3s-1
• Ion – ion recombination Ar+ + Cl- ➔ Ar + Cl 2x10-8cm3s-1
• Ion – molecule reactions H2+ + H2, ➔ H3+ + H 2x10-9cm3s-1
H3+ + H2 + He ➔ H5+ + He keff BIN= k3x[He]
k3<2x10-29cm6s-1
• Attachment CCl4 + e- Cl- +CCl3 ~10-7cm3s-1
• Penning ionization He* + Ar Ar+ + e- + He 7x10-11c .
 Rate coefficients

A+ 3 -1
B products % k[cm s ] T
 km
Reaction Rate of IMR relevant for ionosphere
400 He+
H+ Inosféra
kcoll ~10-9cm3s-1
kIMR 300 N+ O+

F2-max.

He+ + N2
200 O2+ NO+
N+ + O2 1975-90 F-region
+
O2 + NO
O+
+
N2+
N

n+
E-region
100
n-
90

N2+ + O2 80 NO+ electron-ion D-region

1990-00 70
higher
plasma

ion-ion
1 order plasma
+ 3 2 clusters
60 H3O
O+ + O2 H3O+.(H2O)
50 n
101 102 103 104 105 106 cm-
3

O+ + N2
Ion molecule reactions in ISM

Reakce iontů s molekulami

Ion molecule reactions

H3+ in interstellar space

H 2 ⎯cosmic
⎯ ⎯⎯ ray
→ H 2+ + e −

H 2 + H 2+ → H 3+ + H
Very low collision energies

Kr & CCl4

e Cl-
h Kr CCl4
CCl3
Kr+
Electron attachment at very low electron energies
o
10 
5

o
10 
5
Details of Ramsauer effect
Kr
Ne

Ar He
 Total collision and reactive cross sections comparison

Ar
Alkali metals
Ne, He (3eV)

s(v)
(0,3eV)
o
Ar 100 000 
1eV
500A
-
e (v) (3eV) Cs
Ne
(2eV)
Ar CCl4
(0.3eV)
 Reakční rychlost
Značí se v nebo r
1 dni
v=
 i dt

Předpokládáme reakci:
bB+cC➔xX+yY
Stechiometrické koeficienty – obecně i :
 Řád chemické reakce

v = k .c .c ........c
wA
A
wB
B
wR
R

wA , wB ...............wR se určují experimentálně =

reakční řády vzhledem k jednotlivým složkám

Celkový řád chemické reakce

n =  wi
i
Celkový řád reakce a molekularita mají stejnou hodnotu
pouze u elementárních reakcí