HBr, V(m+4) (and E(0)) (Updated 131211; slide: 24-6)

1) KER spectra vs J´ (slides 2-3)2) I(H+ + Br(1/2))/I(H+ + Br(3/2)) vs. J´(slide 4)3) Comparison of KER spectra for E(0) and V(m+4); J´= 1

(slide 5)4) Wavel. Calibr. (slide 6)

Ref:agust-lab-top,C:/…/PPT-131111.pptx

4

3

2

1

0

2.52.01.51.00.50.0 KER/eVAgust,lab top,C:/…/PXP-131111.pxp ; Gr0, Lay1

H+ + Br(1/2)

H+ + Br(3/2)

?

H+ <- HBr+(v´) ?

HBr, V(m+4):

J´=

8

7

6

5

4

3

2

1

0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

0.80.60.40.20.0

Agust,lab top,C:/…/PXP-131111.pxp ; Gr0, Lay1; (<= Agust, Lab top, C:,…./XLS-131111a.xlsx („KER,I,II“ ,“H++Br-“))

H+ + Br(1/2) H+ +

Br(3/2)

?

BLUE sticks:Predicted KERFor 81Br;See next slideBlack sticks:H+ + Br-

J´=

8

7

6

5

4

3

2

1

0

HBr, V(m+4):

KER/eV

0.28

0.26

0.24

0.22

0.20

0.18

86420 J´ Agust,lab top,C:/…/PXP-131111.pxp ; Gr1, Lay0 (<= Agust, Lab top, C:,…./XLS-131111.xlsx

I(H+ + Br(1/2)) I(H+ + Br(3/2))

HBr, V(m+4)

1.0

0.8

0.6

0.4

0.2

0.0

2.52.01.51.00.50.0

E(0) and V(m+4)J´= 1

Agust,lab top,C:/…/PXP-131111.pxp ; Gr2, Lay2

Comparisons of E(0) and V(m+4):

KER/eV

Let´s check wavelengths and wavelength calibrations:

agust, Lab top, C:,…./XLS-131111a.xlsx & XLS-131112.xlsx(„wavel.calibr.“ ))

V(m+4):Comparison of Crete´s wavenumbers and litterature values: correction factor= 2,1359should be subtracted from laser wavenumbers!

J Litterature Crete/lab-book Crete Lab-Lit comment:

2hv/cm-1 l/nm (hv) 2hv/cm-1 cm-1

0 77830 256,941 77834,6095 4,6095

1 77821 256,978 77823,40216 2,402164

2 77803 257,03 77807,65677 4,656769

3 77778,7 257,112 77782,84043 4,140431

4 77743,57 257,226 77748,36596 4,795958

5 77700,09 257,376 77703,05134 2,961338

6 77648,18 257,555 77649,04497 0,864967NB, l/nm; ??

7 77587,92 257,757 77588,18932 0,269316

8 77520 257,983 77520,21625 0,216248

9 77444,97 258,231 77445,76325 0,793246very week; one image

10 77363,66 258,492 77367,56176 3,901758Lab-Lit increases from J´= 9; probably a different system(?)

11 77276,9 258,779 77281,75218 4,852182Lab-Lit increases from J´= 9; probably a different system(?)

refs: https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-130911aka.pptx; slide 12

AK notes, 121113;1

E(0):J´ Litterature Crete/lab-book Crete Lab-Lit

2hv/cm-1 l/nm (hv) 2hv/cm-1 cm-101 77938,8 256,597 77938,96214 0,1621432 77935,6 256,604 77936,8359 1,2358993 77931,6 256,614 77933,79861 2,1986094 77926,5 256,633 77928,02841 1,5284115 77920,6 256,652 77922,25907 1,6590676 77913,5 256,675 77915,27627 1,7762677 77905,4 256,704 77906,47365 1,073658 77895,6 256,734 77897,36959 1,7695889 77883 256,778 77884,02081 1,020811

10 77872,1 256,812 77873,70898 1,60898 strange peakrefs: https://notendur.hi.is/~ag

ust/rannsoknir/Crete/PPT-130911aka.pptx ; slide 10

AK, notes, 121113;1

V(m+5):Litterature Crete/lab-book Crete Lab-Lit

J´= 2hv/cm-1 l/nm (hv) 2hv/cm-1 cm-10 78389,5 255,118 78390,8238 1,3238031 78380,41 255,114 78392,05298 11,64298 ???2 78362,35 255,206 78363,79165 1,4416473 78335,61 255,294 78336,77813 1,1681274 78300,59 255,407 78302,11761 1,52761

ref: https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-130911aka.pptx ; slide 9

AK, notes: 121113;1

agust, Lab top, C:,…./XLS-131111a.xlsx & XLS-131112.xlsx(„wavel.calibr.“ ))

/ Cont.

1.0

0.8

0.6

0.4

0.2

0.0

2.52.01.51.00.50.0

HBrV(m+5) &E(0) & V(m+4)J´= 1

INCORRECTKER predictions forE(0) &V(m+4)See slide 11

Agust,lab top,C:/…/PXP-131113.pxp ; Gr2, Lay2

KER/eV

1.2

1.0

0.8

0.6

0.4

0.2

0.0

2.52.01.51.00.50.0

„V(m+4)“

„J´=10“ isV(m+3), S line, J´= 4See slide 16

„J´=11“

77281,75218

77367,56176

Agust,lab top,C:/…/PXP-131111.pxp ; Gr4, Lay3; numbers: …XLS-131111.xlsx

„J´=11“ is a Rydb.State (possibly F1D2(v´=0))S line, J´= 7)See slide 16

KER/eV

1.2

1.0

0.8

0.6

0.4

0.2

0.0

0.60.50.40.30.20.10.0

„V(m+4)“

„J´=10“ isV(m+3), S line, J´= 4See slide 16

77281,75218 cm-1

77367,56176 cm-1

Agust,lab top,C:/…/PXP-131111.pxp ; Gr4, Lay3; numbers: …XLS-131111.xlsx

„J´=11“ is a Rydb.State (possibly F1D2(v´=0)S line, J´= 7)????See slide 16

KER/eV

250

200

150

100

50

0

-50

x103

77.4077.3577.3077.2577.20x10

3

i3 Q

P

R

S

O

S

E1

Q

F1 S

2 3 4 5 6

V1

(m+3) Q

O

S

V1

(m+5) Q

V1

(m+6) Q

S

O

i3 QV1

(m+4) Q

P

F1 ???S(2)?

S(3)?

S(4)?;77369 cm-1

Q(0)

Q(1)

Q(2)Q(3)Q(4)

Q(2)Q(3)

Q(4)Q(5)

Q(6)

Q(7)Q(8)

Q(9)Q(10)

P(2)P(3)

P(4)P(5)P(6)P(7)

012345678901234567

Agust,lab top,C:/…/HBr 77180_79080-131114ak.pxp ; Gr1, Lay0

Ryd. State77282 cm-1

H79Br+

79Br+

H+

H81Br+

81Br+

V(m+3)

HBr, REMPI spectra (from Iceland):

2hv

1.2

1.0

0.8

0.6

0.4

0.2

0.0

0.60.50.40.30.20.10.0 KER/eV

„J´=10“ isV(m+3), S line, J´= 4See slide 16

77281,75218 cm-1

77367,56176 cm-1

Agust,lab top,C:/…/PXP-131111.pxp ; Gr4, Lay3; numbers: …XLS-131111.xlsx; predictions: XLS-131114.xlsx

„J´=11“ is a Rydb.State J‘‘= 7!

J´= 5,6,7,8,9

J´= 5,6,7,8,9

Red=predictions

800

600

400

200

0

x103

82.1882.1682.1482.1282.10x10

3

Br4D(5/2)<-<-2P(3/2)

243,483 nm 41070,63 82141,26 4D(5/2) 0,5 85826,498 on HBr resonance

agust,labtop,C:/…HBr82100_82400.pxp XLS-131114.xlsx

250,954 39847,95 79695,89 2P(3/2) 1,5 79695,89 on HBr resonance

https://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp136-214315-12.pdf XLS-131114.xlsx

Br2P3/2 <-<- 2P3/2

251,8389 39707,93 79415,85 2P(1/2) 0,5 83101,09

https://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp136-214315-12.pdf XLS-131114.xlsx

Br2P1/2 <-<- 2P1/2

KER (Br) vs various Br+ formation channels:

See agust-labtop,C:/…/XLS-131114.xlsx

Max:

KER(81Br)eV

0,0351970,03524

0,0353070,0353960,0355090,0356440,035801

0,035980,0361770,036403

81Br KER 81Br KERKER(Br(3/2)) KER(Br(1/2))eV eV

0,013269482 0,0076973880,013317537 0,0077454430,013390194 0,00781810,013487191 0,0079150970,013608705 0,0080366120,013754375 0,008182282

0,01392428 0,0083521860,014117805 0,0085457110,014334023 0,008761930,014576229 0,009004135

81Br KER 81Br KERKER(Br(3/2)) KER(Br(1/2))eV eV

0,072191331 0,0666192370,072236967 0,066664873

0,0723066 0,0667345060,072399741 0,0668276470,072516795 0,0669447010,072657098 0,0670850040,072820878 0,0672487850,073006995 0,0674349010,073213688 0,0676415940,073447652 0,067875558

123456789

10

J´

HBr, E(0)

agust-labtop,C:/ …/XLS-131114.xlsx

Br**(Ry) Br/Br*- 1hv Br/Br* - 2hv(3hv)

78.6

78.4

78.2

78.0

x103

0.4 0.3 0.2 0.1 0.0

V(m+5)

V(m+4)

E(0)

J´=

8

6

3

1

J´=8

6

1

J´=3

1

HBr energetics

H* + Br(3/2)H+ + Br-

Ry V/Ion-pair

[ 4P,5s ] 3P

H* + Br*(1/2)

[22P]..

[ B2S ]..

H + Br**(5s)

H+ + Br*(3/2)

HBr energetics

H* + Br(3/2)H+ + Br-

Ry V/Ion-pair

[ 4P,5s ] 3P

H* + Br*(1/2)

[22P]..

[ B2S ]..

H + Br**(5s)

H+ + Br*(3/2)

HBr+(v+)

? Or direct HBr+ formation

HBr energetics

H* + Br(3/2)H+ + Br-

Ry V/Ion-pair

[ 4P,5s ] 3P

H* + Br*(1/2)

[22P]..

[ B2S ]..

H + Br**(5s)

H+ + Br*(1/2)

1.6x105

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Ene

rgy

/cm

-1

543210Internuclear Distance / Å

HBr X1

H+Br

- V

1

HBr**

H1

F1

HBr+ X

2

HBr+* A

2

t3

a3 a

3

HBr* A1

E1

Agust-labtop,C:/../Fig.1-HBrFvsV-papera.pxp

H + Br**(5s)

Br*(1/2)

Br(3/2)

H*(n=2)+Br

H+ + Br-

H+Br+ + e

H++Br+e

1.5x105

1.0

0.5

0.0

Ene

rgy

/cm

-1

543210Internuclear Distance / Å

HBr X1

H+Br

- V

1

HBr**

H1

F1

t3

a3 a

3

HBr* A1

E1

Agust-labtop,C:/../Fig.1-HBrFvV-paperb.pxp

H + Br**(5s)

Br*(1/2)

Br(3/2)

H*(n=2)+Br

H+ + Br-

H+Br+ + e

H++Br+e

[(3)2P] ..superexcited state

[B2S+] ..superexcited state

[4P,5s] Rydb.

HBr+(X)

HBr+*(A)

1.6x105

1.4

1.2

1.0

0.8

Ene

rgy

/cm

-1

543210Internuclear Distance / Å

HBr X1

H+Br

- V

1HBr**

H1

F1

t3a

3a3

HBr* A1

E1

H++Br+e

[(3)2P] ..superexcited state

[B2S+] ..superexcited state

H + Br**(5s)

H*(n=2)+Br

H+ + Br-

H+Br+ + e

[4P,5s] Rydb.

HBr+(X)

HBr+*(A)

0.6

0.5

0.4

0.3

0.2

0.1

0.0

86420 J´ https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131211a.pxp ; Gr5, Lay4

I(H+ <- HBr+(v+)) I(H+ + Br(3/2))

https://notendur.hi.is/~agust/rannsoknir/Crete/XLS-131211.xlsx

ratio

0.4

0.3

0.2

0.1

0.0

78.678.478.278.0x10

3

https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131211.pxp; Gr3, Lay3

I(H+ + Br(1/2)) I(H+ + Br(3/2))

V(m+4)

V(m+5)

E(0)

J´=0

J´=1

J´=0

E(J´)

ratio

0.8

0.6

0.4

0.2

0.0

78.678.478.278.0x10

3

I(H+ <- HBr+(v+)) I(H+ + Br(3/2))

https://notendur.hi.is/~agust/rannsoknir/Crete/E0-KER-131211b.pxp; Gr3, Lay3

V(m+4)

V(m+5)

E(0)

J´=0

J´=0

J´=1

E(J´)

ratio