PHOTOFRAGMENTATIONS, STATE INTERACTIONS AND ENERGETICS OF HALOGEN CONTAINING MOLECULES: TWO-DIMENSIONAL (2+n) REMPI ÁGÚST KVARAN, et al. Science Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, Iceland. Oral presentation at PSI / SLS, June, 2012.

Voltage devider HV - 2Kv RX nozzle Turbo Pump TOF lense MCP detector oscilloscope computer Excimer Laser In out Dye- Laser SHG Time delay  S laser control Pellin Broca prism SHG control In out

REMPI = Resonance Enhanced MultiPhoton Ionization 1xh 2xh 2 E AB AB + + e AB** (2 + 1) REMPI

REMPI = Resonance Enhanced MultiPhoton Ionization 1xh 2xh 2 E AB AB + + e AB** A + B + + e

REMPI = Resonance Enhanced MultiPhoton Ionization 1xh 2xh 2 E AB AB + + e AB** A + B + + e AB # # AB + + e A + + B + e A + B + + e

A + B/B* REMPI = Resonance Enhanced MultiPhoton Ionization 1xh 2xh 2 E AB AB + + e AB** A + B + + e AB # # AB + + e A + + B + e A + B + + e A + + e B + + e

(2 + n)REMPI; n = 1,2, A B AB / Mw I(M + ) Laser excitation / cm -1 2D - REMPI PHOTOFRAGMENTATIONS, STATE INTERACTIONS ENERGETICS

I. Small molecules: Diatomic molecules Linear molecules II. “Bigger molecules” Polyatomic molecules Data:Rotational (J) structure resolution Data: Vibrational (v) structure resolution Analysis (J-dependent): Signal Intensities Power dependences Line-shifts Line-widths Analysis (v-dependent): Signal intensities Power dependences Results (J-dependent): Energetics n,(2+n) State interactions Photofragmention Lifetimes Results (v-dependent): Energetics n,(2+n) State interactions Photofragmention

Intensity Mw H+H+ 35 Cl + H 35 Cl + H 37 Cl + 12 C + Two photon resonance excitation= cm -1 Mass spectrum RCl = HCl

Mw / rel. 35 Cl + H 35 Cl + H 37 Cl + 2xhv Mw 35 Cl + 37 Cl + H 37 Cl + H 35 Cl + /cm -1

r(H-X) Energy HX H X ** H + --X - HX + H + X + e-e- e-e- + HX REMPI: IE limit v´ J´ v´ J´

270 cm -1

V 1  + (v´=m+10)

H 35 Cl + 35 Cl + Q J´=J´´ = HCl, F 1  2 2h  / cm -1 Intensity

r(H-X) Energy HX H X ** H + --X - HX + / HX + H + X + e-e- e-e- + HX REMPI: IE limit v´ J´ v´ J´

State Interactions ? (1) /  0 (2) /  0 12  c 1  0 1  a  c 2  0 2 = +  b =  c 1 ´  0  c 2 ´   c 1  c = 1 E

W 12 : Interaction strength (1) /  0 (2) /  0 12  c 1  0 1  a  c 2  0 2 = +  b =  c 1 ´  0  c 2 ´   c 1  c = 1 E

(1) /  0 (2) /  0 12  c 1  0 1  a  c 2  0 2 = +  b =  c 1 ´  0  c 2 ´   c 1  c = 1 E( ) E( J´ ) EE E

H 35 Cl + 35 Cl + Q J´=J´´ = HCl, F 1  2 2h  / cm -1 Intensity

x  E J´=8 = 11.3 cm -1 HCl: F 1  2 V 1   c 1 2  c 2 2 X ?

H 35 Cl + 35 Cl + Q J´=J´´ = HCl, F 1  2 2h  / cm -1 Com- press- ion E x p a n s i o n Intensity



x  E J´=8 = 11.3 cm -1 HCl: F 1  2 V 1   c 1 2  c 2 = X? 6 cm -1 from line shifts

r(H-X) Energy HX H X ** H + --X - HX + / HX + H + X + e-e- e-e- + HX REMPI: IE limit v´ J´ v´ J´ c1c1 2 c2c2 2 ? X +

r(H-X) Energy HX H X ** H + --X - HX + / HX + H + X + e-e- e-e- + HX REMPI: v´ J´ v´ J´ H + X X+X+

r(H-X) Energy HX H X ** H + --X - HX + / HX + H + X + e-e- e-e- + HX REMPI: v´ J´ v´ J´ HX*** H + X* X+X+

r(H-X) E HX H + --X - HX + / HX + H + X + e-e- HX REMPI: v´ J´ v´ J´ c1c1 2 c2c2 2 X+X+ X X* c1c1 c2c I (HX + ) = c1c1 c2c I (X + ) = Ry:I.P./V: c2c2 2 c2c2 2 == X+)/X+)X+)/X+)  =    X + ) /    X + )  = X+)/X+)X+)/X+)

r(H-X) E HX H + --X - HX + / HX + H + X + e-e- HX REMPI: v´ J´ v´ J´ c1c1 2 c2c2 2 X+X+ X X* c2c2 2 c2c2 2   = X+)/X+)X+)/X+)   = X+)/X+)X+)/X+)

Exp.Q i=35i=37 I( i Cl + )/I(H i Cl + ) Exp.Q Calc. V,v´ = 20 Calc. V,v´=20 j 3  - 1 ; ´=0 isotopomersH 35 ClH 37 Cl J´ closest resonances(J´ res )22 |  E(J´ res ) | / cm W 12 (J´ res ) / cm c 1 2 (c 2 2 ) (J´ res )0.89(0.11)0.81(0.19)   14 x x H i Cl j 3  - 1 > > <   K. Matthíasson et al. J. Chem. Physics, 134, , (2011)

r(H-X) Energy HX HX** H + --X - HX + / HX + H + X + e-e- HX REMPI: v´ J´ v´ J´ H + X X+X+ j 3  - 1 t 3  + 1 S/O

H 35 Cl f 3  2 f 3  1 I( 35 Cl + )/I(H 35 Cl + ) States f32f32 f31f31 J´ closest resonances(J´ res )56 |  E(J´ res ) | / cm W 12 max (J´ res )/ cm c 1 2 (J´ res )  00 1.0 x < > Exp.Q Calc. V,v´=9 Exp.S Calc. V,v´=8 <

H 35 Cl f 3  2 f 3  1 I( 35 Cl + )/I(H 35 Cl + ) Exp.Q Calc. V,v´=9 Exp.S Calc. V,v´=8  No dissociation No predissociation pathway Dissociation: Predissociation by S/O couplings via “Gateway Rydberg states ( 1 , 3  )” :

H 37 Cl j 3  - (0 + ) Exp. Q

J´=0 J´=6 J´=6 v´=21 J´=6 v´=20 J´=0 : : j 3  - (0 + ), v´=0 V 1  (0 + ) H 37 Cl Near resonance  S  ´=0 E/cm -1

Calc. V,v´=20 V,v´=21 H 37 Cl j 3  - (0 + ) Exp. Q V´ statesv´=20v´=21 J´ closest resonances(J´ res )6 |  E(J´ res ) | / cm W 12 (J´ res ) / cm c 1 2 (J´ res )0.82  4.0(52 x )

H 79 Br

J´=0 J´=6 J´=9 J´=6 v´=m+5 H 79 Br E 1  (0 + ), v´=0 J´=9 v´=m+4 J´=0 V 1  (0 + ) Off resonance S S  ´=0 J´=6 J´=0 E/cm -1

H 79 Br, E(v´=0) I( 79 Br + )/I(H 79 Br + ) Linewidth/ cm -1

G(C 1  1 ) (JL) (SO) JL R(t 3  + 1 )R(A 1 , a 3  ) R(t 3  + 1 ) G(C 1  1 ) R(A 1 , a 3  ) V 1  + (m+7) E 1  + (1) F 1   (1) Energy (SO) (JL) (SO) HBr Á. Kvaran et al., J. Chem. Physics, 136, ,(2012)

* - H+H+ X-X- XH HX** { }.. HXHX : : : : : : : “Summary”: Photodissociation, State interactions, Energetics...

: Victor Huasheng Wang Kristján Matthíasson Jingming Long Helgi Rafn Hróðmarsson Coworkers: *... HBr,HI.....HCl, HBr HCl,......RX..

: Kári Sveinbjörnsson Hafdís Inga Ingvarsdóttir Eiríkur Þórir Baldursson Andras Bodi Coworkers: * CH 3 I CF 3 Br Ab initio CH 2 Br 2