hcl agust,heima,...sept10/ahcl(3+1)j3s(0)calc-141210ak.pxp (jms paper)

HCl

agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper)agust,www, ....Sept10/PPT-141210ak.pptagust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp (R-C spectrum)agust,heima,...Sept10/XLS-141210ak.xlsagust,heima,...Sept10/XLS-151210ak.xlsagust,heima,...Sept10/XLS-161210ak.xlsagust,heima,...Sept10/22320_22356-161210ak.pxp (new R-T spectrum)agust, heima,...Sept10/J3S_V1S21-171210ak.pxp (new R-T spectrum)

agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxpagust,heima,...Sept10/XLS-201210ak.xlsagust,heima,...Sept10/Look for J7-201210.pxp

agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 5, Gr:2_1

92.0x103

91.5

91.0

90.5

E/c

m-1

280270260250240230220EJ´,J´-1/cm

-1

56

7

9

10

11

56

7

8

9

1

4

V statev´=24

j statev´=0

13

j state

2

8

0235 46 789 KM´s assignment

JMS, 228,143,(2004)-assignment

REMPI-current

89.2889.2689.2489.22x10

3

HCl(3+1) j3-(0

+) (0,0)

B´=9.654, D´=-0.00039 0=89282

Q peaks from REMPI (2+1)

Q lines from Calc.

P

R

Exp.

Calc.

02456

7 8

91011

1357J''=90123465789 J''

0123=J''

agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp (R-C spectrum), Lay:2, Gr:1

123456 789 0KM´s assignment

JMS, 228,143,(2004)-assignment

J´ (JMS, 2004) J´(KM)

1 0

2 1

3 2

4 3

5 4

8 5

9 6

6 7

7 8

10 9

11 Not seen

NB!: KM´s (REMPI-TOF; R-T) spectrum is a lotcolder than the JMS (20014)-REMPI- current (R-C)spectrum

Now lets try

1) Derive Energy level values both from R-T and R-C spectra using KM´s assignment and check shifts.

2) Insert Wangs and Longs´newest spectra uncluding “newly observed “peaks for comparison.

DE(J´,J´-1)

19.37762

38.54302

57.38401

78.08836

96.34387

112.1383

160.2595

153.4953

174.9333

J´

1

2

3

4

5

6

7

8

9

J nju(Q, j(0+)<-<-X

0 89282

1 89280.5

2 89277.3

3 89272.1

4 89266.8

5 89259

6 89246.3

7 89261.1

8 89248.6

9 89237.1

from KM:

agust,heima,...Sept10/XLS-151210ak.xls

E(J´)=nju(Q)+E(J´´)

89282

89301.37762

89339.92064

89397.30465

89475.39301

89571.73689

89683.87522

89844.13475

89997.63

90172.56329

Slide 6 Slide 7

90.0

89.8

89.6

89.4

x103

806040200

agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 7, Gr:11

E(J´)

J´(J´+1)

Coefficient values ± one standard deviation K0=C = 89281 ± 3.56 K1=B´ = 9.7179 ± 0.229 K2=D´ = 0.0026284 ± 0.0026

J´=7

J´=9

J´=6

From REMPI-TOF (KM):

160

140

120

100

80

60

40

20

8642


E J´,J´-1

J´

DE(J´,J´-1)

19.37762

38.54302

57.38401

78.08836

96.34387

112.1383

160.2595

153.4953

174.9333

J´

1

2

3

4

5

6

7

8

9

= 19.497 J´ = 2B´J´=>B´= 9.7485 cm-1


From REMPI-TOF (KM):

4.8436663 cm-1

23.78

Now let´s look at the latest data for V, v´=21 from Long and Wang:

I will wait for Longs analysis and summaries of mass spectra vs REMPI peaks

Let´s look at the REMPI-current data

Let´s look at energy levels or the V, v´=21 state: Is there a shift of levels to be found?

36

34

32

30

28

26

24

22

20

x103

22.335022.334522.334022.333522.333022.332522.3320x10

3

agust,heima,...Sept10/22320_22356-161210ak.pxp, Lay:0, Gr:1

H+

i=35

i=37

22334.27 89337.08 cm-1V,v´=21, J´=6

V, v´=21

J´ 1hv(Laser) 2hv E(J´´) E(J´)=nju(Q)+E(J´´) DE(J´,J´+1)0 22401.825 89607.3 Green 0 89607.31 22398.275 89593.1 Green 20.87762 89613.97762 6.6776172 22391.15 89564.6 Green 62.62064 89627.22064 13.243023 22380.5 89522 Green 125.2046 89647.20465 19.984014 22366.425 89465.7 Green 208.593 89674.29301 27.088365 22348.925 89395.7 Green 312.7369 89708.43689 34.143876 22334.27 89337.08 Wang 437.5752 89774.65522 66.21833

6 22327.575 89310.3 KM prediction 89747.8752290.78


60

50

40

30

20

10

654321

= 6.8778 J´ = 2B´J´=>B´= 3.4389 cm-1

From REMPI-TOF (VHW&JL):

24.95 cm-1

E J´,J´-1

J´

DE(J´,J´+1)

6.677617

13.24302

19.98401

27.08836

34.14387

66.21833

J´

1

2

3

4

5

6agust,heima,...Sept10/XLS-151210ak.xls


250

200

150

100

50

0

x103

22.35522.35022.34522.34022.33522.33022.325x10

3

KM´s prediction, assuming (J’=6;V)-(J´=6,j)=64cm-1

(W&L´s observation for J´=6 (V)(?):(J’=6;V)-(J´=6,j)=90.8 cm-1)


NB!: According to KM (211210) the peak at 22334.2789337.08 is a S line peak for V!! The broad peaksHowever might be V,v´=21, J´=6

E1(6) 89683.87522see 161210;2E10(6) 89688.71889

DE10(5,6)-DE1(5,6) = D(DE1(5,6)) 4.8436663E2(6) 89774.65522E20(6) 89749.70522D(DE2(5,6)) 24.95

(1/2)(E10(6)+E20(6)) 89719.21205E20(6)-E10(6) 60.9863337

W12(6) 17.85661089cm-1


89.78

89.76

89.74

89.72

89.70

89.68

x103

2.01.51.00.50.0

89683.9 = E1 (6)

89688.7 = E10(6)

89719.2 cm-1

E20(6) = 89749.7

(E2 (6) = 89774.7

4.84 cm-1

24.95cm-1

1

2/1

202

01

2

102

0112

9.17

)6()6()6(2

12

4

1)6(

cm

EEEEEW


?J´(V, v´=21) = 6

J´(j, v´=0) = 6

)NB! Not needed in calculation of W12 (see below)

W12 dervid from J´=6

W12 derived from J´=7 :

60

50

40

30

20

10

7654321J´


E J´,J´-1

J=6 J=7

E1(J) 89683.87522 see 161210;2 89844.13475

E10(J) 89688.71889 89820.35475

DE10(J-1,J)-DE1(J-1,J) = D(DE1(J-1,J)) 4.8436663 23.78

E2(J) 89774.65522 ?

E20(J) 89749.70522 89756.58149

D(DE2(J-1,J)) 24.95 ?

(1/2)(E10(J)+E20(J)) 89719.21205 89788.46812

E20(J)-E10(J) 60.9863337 -63.77326354

W12(J) 17.85661089 45.62912016 V,v´=21 state data

This is largely overestimated value

This is slightly underestimated value

The large difference in W12 obtained for J´= 6 and 7 suggests that the Line assignment for j<-<-X is wrong(?).

Let´s check other possibilities.

1) OLD assignment:

NO evaluation method is no good!

180

160

140

120

100

80

60

40

108642

Old assignmentOLD assignment OLD OLD J´

nju(Q, j(0+)<-<-X E(J´)=nju(Q)+E(J´´)DE(J´,J´+1)

89282 89302.87762 1

89280.5 89343.12064 40.243023 2

89277.3 89402.50465 59.384009 3

89272.1 89480.69301 78.188363 4

89266.8 89579.53689 98.843874 5

89261.1 89698.67522 119.13833 6

89248.6 89831.63475 132.95953 7

89259 90008.03 176.39525 8

89246.3 90181.76329 173.73329 9

89237.1 90379.32473 197.56144 10

20.707

3.27

j,v´=0 state data

OLD assignment gives largest gap for J´=7 <->J´=8 whereasKM´s assignment gives largest gap for J´=6 <->J´=7

Is it possible to find largest gap for J´=5 <->J´=6?That would fit with the V, v´= 21 gap / shifts!

= j state peaks

KM: 9 6 8 5 7 4 3 2 1 0 OLD: 10 11 9 7 8 6 5 4 3 2 1AK(1) 9 5 7 8 6 4 3 2 1 0AK(2) 9 5 8 7 6 4 3 2 1 0AK(3) 8 - 6 - 5 7 4 3 2 1 0AK(4) 9 6 6/8 5 5 7 4 3 2 1 0

Larger Cl+/HCl+ ratios according to KM

Large gap:6<->77<->85<->65<->66<->76<->7

ATH!

NO!910

i=37 J(1);Soverlap

160

140

120

100

80

60

40

20

8642

AK(1) assignment:


NO!

20

15

10

5

x106

22.32222.32022.31822.31622.31422.31222.310x10

3

V1

(0

+)

1

0243567

agust, heima,...Sept10/J3S_V1S21-171210ak.pxp; Lay: 2, Gr: 1

1hv

H+

H35Cl+

35Cl+

H37Cl+

J, v´=0Could be 37 peak from V, v´=21

160

140

120

100

80

60

40

20

8642

AK(2) assignment (see slide 19):

agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 11 Gr:15

NO!

agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 12, Gr:16 and .....Sept10/XLS-201210ak.xls

90.2

90.0

89.8

89.6

89.4

x103

2.01.51.00.50.0

Energy levels (E(J´):

J(0+)-state <= KM

J´=7 J´=7

J´=6

J´=6

89828.476

89844.13475

89799.8784

Diff = 15.65875

Prediction for E(J´=7): 89784.21965

89201.1849

J´´=7 -> J´(V) = 7): 89201.1849=

4 x 22300.296

i.e. difference between peaks for J´=7: 59.5 cm-1

13.018 cm-1

V,v´=21 state

160

140

120

100

80

60

40

20

87654321

AK(3) assignment (see slide 19):

agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 13 Gr:17

90.2

90.0

89.8

89.6

89.4

x103

2.01.51.00.50.0

J(0+)-state <= AK(3)

V,v´=21 state

12.298 cm-1

J´=7

J´=6


Now it is possible to predict the position of the J´=9 band

nju = 89224.802E(J´) = 90160.26529 (see next slide)Now let´s check position on a spectrum:

It could indeed be the peak which Wang thinks that is J´=7 for the V state which is found at 89227.19!!!

Lets try that

agust,heima.....Sept10/XLS-201210ak.xls

90.2

90.0

89.8

89.6

89.4

x103

2.01.51.00.50.0

Fits nicely

J´=7

J´=6

J(0+)-state <= AK(3)


300

200

100

0

x103

89.2689.2589.2489.2389.22x10

3

J'=7 (?)

agust,heima,...Sept10/Look for J7-201210.pxp

9 8

6

5

7

This could be V, v´=21, J´=7(?)

4.02

6 78

95

See also figs in KM´s manuscript and my comments there.

It is worth performing some isotopomer calculations

NB! According to Longs estimate (agust,heima,..../Sept10/V state V21q energy diference between H35Cl and H37Cl-141210jl-201210ak.xls)The isotope separation for J´= could be < 5.

Now let´s check where exactly j(1), S serie peak is to be found.

hcl agust,heima,...sept10/ahcl(3+1)j3s(0)calc-141210ak.pxp (jms paper)

Documents

j0 agust

rc spectra

kms rempitof rt spectrum

rc spectrum

new rt

xlsfrom rempitof

rempitof vhwjl

sept10 lay