![Page 1: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/1.jpg)
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
![Page 2: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/2.jpg)
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
![Page 3: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/3.jpg)
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
![Page 4: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/4.jpg)
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
![Page 5: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/5.jpg)
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
![Page 6: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/6.jpg)
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):
![Page 7: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/7.jpg)
160
140
120
100
80
60
40
20
8642
agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 6, Gr:9
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
agust,heima,...Sept10/XLS-151210ak.xls
From REMPI-TOF (KM):
4.8436663 cm-1
23.78
![Page 8: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/8.jpg)
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
![Page 9: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/9.jpg)
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?
![Page 10: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/10.jpg)
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
![Page 11: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/11.jpg)
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
agust,heima,...Sept10/XLS-161210ak.xls
![Page 12: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/12.jpg)
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
agust,heima,...Sept10/22320_22356-161210ak.pxp, Lay:1, Gr:2
![Page 13: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/13.jpg)
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)
agust,heima,...Sept10/22320_22356-161210ak.pxp, Lay:0, Gr: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
![Page 14: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/14.jpg)
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
agust,heima,...Sept10/XLS-161210ak.xls
![Page 15: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/15.jpg)
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
agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 8, Gr:12
?J´(V, v´=21) = 6
J´(j, v´=0) = 6
)NB! Not needed in calculation of W12 (see below)
W12 dervid from J´=6
![Page 16: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/16.jpg)
W12 derived from J´=7 :
60
50
40
30
20
10
7654321J´
agust,heima,...Sept10/22320_22356-171210ak.pxp, Lay:1, Gr:2
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
![Page 17: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/17.jpg)
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!
![Page 18: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/18.jpg)
180
160
140
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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
![Page 19: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/19.jpg)
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
![Page 20: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/20.jpg)
160
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40
20
8642
AK(1) assignment:
agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp, Lay: 10, Gr:14
NO!
![Page 21: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/21.jpg)
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
![Page 22: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/22.jpg)
160
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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!
![Page 23: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/23.jpg)
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
![Page 24: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/24.jpg)
160
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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
![Page 25: HCl agust,heima,...Sept10/aHCl(3+1)j3S(0)Calc-141210ak.pxp (JMS paper) agust,www,....Sept10/PPT-141210ak.ppt agust,heima,...Sept10/HCl(3+1)j3Sigma(0) Calc-141210ak.pxp](https://reader035.vdocuments.pub/reader035/viewer/2022062320/56649d535503460f94a2eeda/html5/thumbnails/25.jpg)
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
agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 12, Gr:16 and .....Sept10/XLS-201210ak.xls
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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
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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)
agust,heima,....Sept10/aHCl(3+1)j3S(0)Calc-201210ak.pxp, Lay: 12, Gr:16 and .....Sept10/XLS-201210ak.xls
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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
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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.