HBr; Updated: 22.11.2013

Imaging experiments in Crete

Labtop..C:……/Crete/HBr/PPT-130911aka.pptx

&

https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-130911aka.pptx(updated file)

30 k

60 k

90 k

H + Br30300 cm-1

93736.45 cm-1

H + Br**(4P;5s)

Lowest energy Br**

HBr+ + e; 94205.51806 cm-1 (11.68 eV)

H + Br*(1/2)33985.24 cm-1

H + Br +125584.8

139978.77 H + + Br

74000 cm-1 (9.17 eV)

86000cm-1 (10.66 eV)

43000cm-1( 232.56 nm <= 465.11 nm)37000cm-1 (270.27 nm <= 540.54 nm)

Total scanrange for HBr H + + Br-112849.6cm-1

130 k

(1)

(2)

(3)

(n) = number of photons

https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PPT-180112ak.ppt

Energetics: cm-1

„Internuclear distance“

https://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf

III. Different ion formation channels:

Main channels:HBr**(Ry,v´,J´) + hv -> HBr+ + e ; Ionization of Rydberg stateHBr**(I-P,v´,J´) + 2hv -> -> H+ + Br + e; Ionization of Ion-pair statesHBr**(I-P,v´,J´) + 2hv ->-> H + Br+ + e; Ionization of Ion-pair states

Other possible channels(?):HBr**(I-P,v´,J´) + hv -> -> H+ + Br-; Ionization of Ion-pair states ; Ion- Pair formationBr/Br* + 3hv ->->-> Br+ + e; Ionization of Br atoms; Br+ formationHBr**(I-P,v´,J´) + hv-> HBr+ + e Ionization of Ion-pair states ; Parent ion formationHBr**(Ry,v´,J´) + 2hv -> H+ + Br + e ; Ionization of Rydberg state; H+ formation:?=> Number of different states and J´ dependent ion formation channels

I. 2hv resonance excitations:HBr + 2hv ->-> HBr**(Ry,v´,J´); Rydberg state excitationHBr + 2hv ->-> HBr**(I-P,v´,J´); Ion-Pair state excitation

II. Intersystem crossings:HBr**(Ry,v´,J´) HBr**(I-P,v´,J´); Rydb. – Ion pair interactions DE(J´Ry,J´IP) dependentHBr**(Ry,v´,J´) ->-> H + Br/Br*; Predissociation

Our recent mass resolved REMPI and perturbation studies (summary):

Paper: Resonance excitation Range:

HBr States1: Comments:

http://jcp.aip.org/resource/1/jcpsa6/v138/i4/p044308_s1?isAuthorized=no or https://notendur.hi.is/~agust/rannsoknir/papers/jcp138-044308-13.pdf(JCP; 2013)

77520 – 78450 cm-1/9.61-9.73 eV

E (v´= 0) vs.V(v´=m+4) andV(m+5)

Strong Rydberg to ion-pair interaction;Emphasize J´ dependence

http://jcp.aip.org/resource/1/jcpsa6/v136/i21/p214315_s1?isAuthorized=no (JCP, 2012)

79040-80300 cm-1/9.80 – 9.96 eV

a) F1D2(v´=1) vs. V(v´=m+7)

b) E(v´=1) and H(v´=0) vs. V(v´=m+7) & V(v´=m+8)

a) (weak) resonance interactions

b) Strong interactions

Emphasize J´ dependence

http://www.sciencedirect.com/science/article/pii/S0022285212002019 ORhttps://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp136-214315-12.pdf (JMSp, 2012)

74000 – 86000 cm-1/9.17 – 10.66 eV

Variour Rydberg and ion-pair states

„total range“Spectroscopic parameters and „New states“

1. V(v´): Ion-pair states; E(v´),H(v´),F(v´): Rydberg states

Others (H.P. Loock et al.) „imaging studies“ on HBr:

Paper: Resonance excitation Range:

HBr States1: Comments:

https://notendur.hi.is/~agust/rannsoknir/papers/HBr/pccp8-2940-06.pdf

(2006)

75816 – 80655 cm-19.4 – 10 eV

Many (i,F,E,H, V) Photoelectron detection. Focus on photoionization dynamics. Discover autoionization effects; Do not deal with J´dependences

https://notendur.hi.is/~agust/rannsoknir/papers/jcp127-124304-07a.pdf

(2007)

Specific wavelengths (see next column)

Q(0) and Q(1) lines for E(v´=0), H(v´=0), V(v´= m+3, m+i;i=5-8)

H+ detection; emphasize electronic state effects and v´dependences for V states; Do not deal with J´dependences

1. V: Ion-pair states; E,H,F, i: Rydberg states

Suggestions for experiments:-relevant to our studies (see above):

1) Studies relevant to strong state interactions vs. J´(http://jcp.aip.org/resource/1/jcpsa6/v138/i4/p044308_s1?isAuthorized=no /JCP; 2013)(or https://notendur.hi.is/~agust/rannsoknir/papers/jcp138-044308-13.pdf)Record ion images (H+, Br+, HBr+ (?)) vs J´ for two-photon, one-color resonance excitations to J´ levels ofa) The Rydberg state E(v´=0); For Q lines, J´=0, 2, ..8, 9(?) b) The Ion-pair state V(v´=m+5); For Q lines, J´=0, 2, ..8, 9(?) c) The Ion-pair state V(v´= m+4); For Q lines, J´=0, 2, ..8, 9(?) (excitation range: 77520 – 78450 cm-1/9.61-9.73 eV; photons: 258.00-254.94 nm;see lines: https://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf and/orhttps://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms90-152-81.pdf)

::

2) Studies relevant to i) weak resonance state interactions and ii) strong interactions vs. J´(http://jcp.aip.org/resource/1/jcpsa6/v136/i21/p214315_s1?isAuthorized=no /JCP, 2012)(or https://notendur.hi.is/agust/rannsoknir/papers/HBr/jcp136-214315-12.pdf ) Record ion images (H+, Br+, HBr+ (?)) vs J´ for two-photon one color resonance excitations to J´ levels ofa) The Rydberg state F(v´=1); Q lines, J´=3, 4,5,6,7 (i)b) The Rydberg state E(v´=1); Q lines, J´= 0,1,….7(?) (ii)c) The Rydberg state H(v´=0), Q lines, J´= 0,1,….9(?) (ii)d) The Ion-pair state V(v´=m+7), Q lines, J´= 0,1, ..(5),..9 (i and ii)e) The Ion-pair state V(v´=m+8), Q lines, J´= 0,1,…7 (ii)(excitation range 79040-80300 cm-1/9.80 – 9.96 eV; photons: 253.04-249.07 nm;see lines: http://jcp.aip.org/resource/1/jcpsa6/v136/i21/p214315_s1?isAuthorized=no and/orhttps://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf and/orhttps://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms90-152-81.pdf)

See spectral lines below:

http://jcp.aip.org/resource/1/jcpsa6/v136/i21/p214315_s1?isAuthorized=no

O Q(J´=J´´) S

https://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf

J´ Q0 78389,51 78380,412 78362,353 78335,614 78300,595 78257,836 782087 78151,928 78090,539 78024,92

Predicted lines fromB´,D´, n0, B´´,D´´See:„C:…Vm4Qlines-130916ak.xlsx

https://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf

O Q (J´=J´´) S O Q (J´=J´´) S

Q:J´= J´´

https://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf

O P Q(J´=J´´) R S

Q:J´= J´´

https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms90-152-81.pdf1hv absorption => Q lines not observed

J´ Q0 778301 778212 778033 77778,74 77743,575 77700,096 77648,187 77587,928 775209 77444,9710 77363,6611 77276,912 78481,62

See:„C:…Vm4Qlines-130916ak.xlsx

Q:J´= J´´

From ourREMPI spectra

https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms90-152-81.pdf1hv absorption => Q lines not observed

https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms90-152-81.pdf1hv absorption => Q lines not observed

http://jcp.aip.org/resource/1/jcpsa6/v138/i4/p044308_s1?isAuthorized=no

REMPI Spectra:

http://jcp.aip.org/resource/1/jcpsa6/v136/i21/p214315_s1?isAuthorized=no

https://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf

More V(m + i) lines:See Table IV in https://notendur.hi.is/~agust/rannsoknir/papers/jcp93-4624-90.pdf (C&G; 1990)and Table 3 in https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms282-20-12.pdf (Long et al. (2012)and Table III in https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms90-152-81.pdf (G,G&T; 1982)

C&G(90) GGT(82) Long et al.(12)P&R: V(m-1)V(m)V(m+1)

V(m+2) V(m+2)V(m+3) V(m+3)

V(m+4)V(m+5) V(m+5)V(m+6) V(m+6)V(m+7) V(m+7)V(m+8) V(m+8)-------V(m+10)

V(m+11) V(m+12) V(m+12)

V(m+13) V(m+13)----------V(m+16)V(m+17) V(m+17)

V(m+18)V(m+19)

https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms282-20-12.pdf

Alternative HBr experiments(3 & 4):

3) „near-resonance“ interaction: k3P1(v´= 0) (k(0)) and V(m+9) for J´= 7Ref: https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms282-20-12.pdf :

4) „near-resonance“ interaction: 6pp3S-(v´= 0) and V(m+17) for J´= 7,8,9Ref: https://notendur.hi.is/~agust/rannsoknir/papers/HBr/jms282-20-12.pdf :

O Q S