PhD project overview -REMPI analyses of small,

iodine containing molecules

Helgi Rafn Hróðmarsson

Presentation overview

• Introduction• Courses• Project overview• Publications &

conferences• Timeline

• Experimental• Theory (diet)• Findings

– New states– State Interactions

Introduction

• Summer internship at Prof. Kvaran‘s research group summers 2009 & 2010.

• Study.is – private tutoor since november 2010.

• B.Sc. Project under Prof. Kvaran‘s supervision spring 2011.

• B.Sc. degree in 2011.• CRI – research & development.• Started as M.Sc. January 2012.• Subsequently switched to PhD.• Plan on finishing late 2015 /

early 2016.

Courses

• Finished courses– Astrophysics 1 (6 ECTS)– Organic Chemistry 3 (6 ECTS)– Inorganic Chemistry 3 (6 ECTS)– Inorganic Chemistry 3 labwork (4

ECTS)– Mathematical analysis IIIB (6 ECTS)– Mathematical analysis IVB (6 ECTS)– Málstofa (1 ECTS)– Total (35 ECTS)

• Courses for this semester– Quantum Physics 1 (8 ECTS)– Computational Chemistry (10

ECTS)– Total (18 ECTS)

• Grand total (53 ECTS)

• Course next semester – Inorganic chemistry 4 (10 ECTS)?– Málstofa (1 ECTS)

• Other interesting courses – Modern optics (8 ECTS)– Quantum Physics 2 (8 ECTS)– Astrophysics 2 (8 ECTS)– Electromagnetism (8 ECTS)– Reading course (10 ECTS)

Project Overview

• REMPI of HI– New states– State interactions

• REMPI CH3I

• REMPI of I2?

• More?

• Puplished papers• Jingming Long, Helgi Rafn Hróðmarsson, 

Huasheng Wang and Ágúst Kvaran, "Photofragmentations, State Interactions and Energetics of Rydberg and Ion-pair states: Two Dimensional Resonance Enhanced Multiphoton Ionization of HBr via singlet-, triplet-, W = 0 and 2 states.  J. Chem. Phys., 136, 214315, (2012)

• Helgi Rafn Hróðmarsson, Huasheng Wang and Ágúst Kvaran, New REMPI observations and analysis.for Rydberg and Ion-pair states of HI.  J. Molecular Spectroscopy, 290, p:5-12,  (2013)

• In preparation• Helgi Rafn Hróðmarsson, Huasheng Wang and 

Ágúst Kvaran,  "Photofragmentations, State Interactions and Energetics of Rydberg and Ion-pair states: REMPI of HI" 

Future publications

• Paper– i) HI – new states #2– ii) HI – state

interactions #2– iii) Overview paper

summerizing the results of REMPI of HCl, HBr, and HI.

– iv) Methodology of spectra assignment for HX‘s?

• Timeline– Fall 2013– Fall 2013

– Spring/summer 2014

– Spring/summer 2014

Future conferences

• EFNÍS conference – October 2013 - Reykjavík

• Annual meeting of the Spectroscopy and Dynamics Interest Group of the Royal Society of Chemistry – January 2014 – Oxford

Project timeline2012a 2012b 2013a 2013b 2014a 2014b 2015a 2015b 2016a

Experiments – HI Data analysis – HI Experiments – CH3I (I2?)

Data analysis – CH3I

Data analysis – I2?

Go abroad?

Write thesis

The project

• Two photon excitation to Rydberg and ion-pair states in HI.

• Spectra assignments, location of new spectra, previously unobserved, either or both in absorption spectroscopy and REMPI.

• Identification and classification of spectral perturbations (via line shifts, intensity alterations and line width deviation)

• Excitations in CH3I

• Further specifications in analyses pending.

• I2?

• Other?

Experimental setup

The project

• From a chemist‘s point of view.– Molecular orbitals.– HOMO & LUMO

-25

-20

-15

-10

E /

eV

H I

1s

5s

5p

(n)

(b)

* (a)

(n)

HI

The project

• From a physicist‘s point of view.

• Hamiltonians• Harmonic oscillator• Rigid Rotor

-25

-20

-15

-10

E /

eV

H I

1s

5s

5p

(n)

(b)

* (a)

(n)

HI

80x103

60

40

20

0

E [

cm-1

]

4.54.03.53.02.52.01.51.0

r [Å]

'' = 0

'' = 1

Ion-pair stateRydberg state

Ionization potential - 83768.7 cm-1

Repulsive state

Findings so far (new states)

• New states:• Spectra due to two-photon resonance transitions to Rydberg states

not previously detected in REMPI but identified in single-photon absorption studies {k3Π0(ν’ = 1) and k3Π1(ν’ = 1)}.

• Spectra due to two-photon resonance transitions to Rydberg states, not previously detected {d3Π0(ν’ = 1)}.

• Spectra due to two-photon resonance transitions to ion-pair states, not previously detected in REMPI but identified in single-photon absorption studies {V1Σ+(ν’ = m + 8) and V1Σ+(ν’ = m + 9)}.

• Spectra due to two-photon resonance transitions to ion-pair states not previously detected {V1Σ+(ν’ = m + 7)}.

Re

lative

in

ten

sity /a

.u.

71.12x10371.1071.0871.0671.0471.0271.0070.98

Wavenumber /cm-1

k31('=1)

d30('=1)

P QR

Q

1

1111 2 3 4 5 6

1 0 07

H+

I+

HI+

2[3]°5/2 I(

2P1/2)

Rel

ativ

e in

tens

ity /a

.u.

70.36x10370.3470.3270.3070.2870.26

Wavenumber /cm-1

F 12('=0)

S

R

3 4

4 5 6 7 8

Q012345

k 30('=1)

HI+

I+

H+

2 5 6

932

20x103

15

10

5

0

Rela

tive inte

nsity /

a.u

.

72.00x10371.9571.9071.85

Wavenumber /cm-1

V 1

('=m+9)

V 1

('=m+8)

Q

Q

01234567

012345

Other findings in our recent publication

• Reassignment of the E and H states.

• Assignment of the O1Σ+ state.

• Off-resonance interactions leading to the „clenching“ of the V(m+8) ion-pair state.

72.4x103

72.2

72.0

71.8

71.6

71.4

71.2

71.0

Wav

enum

ber

/cm

-1

V 1

+('=m+7)

V 1

+('=m+8)

V 1

+('=m+9)

O1

+ ('=0)

E 1

+('=2)

J'

9

:

0

9

0

:

J'

0

11

03

:

Findings so far (state interactions) – has yet to be

published• Both off-resonance and near-resonance

interactions between– H1Σ+(1) Rydberg state and the V(m+6) ion-pair

state.– O1Σ+(0) Rydberg state and the V(m+7) ion-pair

state.

• Near-resonance interactions between the I1Δ2(0) Rydberg state and the V(m+9) ion-pair state.

Rel

ativ

e in

tens

ity /

a.u.

70.95x10370.9070.8570.80

Wavenumber /cm-1

H1

+('=1)

Q05 4 ...

67

89

O012

m32('=0)

R

2 3 4 5

S2 3 4 5

S2 3 4 V

1

+('=m+6)

Q0123456

78

Q26

H+

I+

HI+

10

2P1/2

2[1]°3/2

2P1/2

2[0]°1/2

Rela

tive in

tensi

ty /

a.u

.

71.45x10371.4071.3571.3071.2571.20

Wavenumber /cm-1

O1

+('=0)

Q07

814

S2 3 4 5 6 7 8

V1

+('=m+7)

Q0123456

78

O

012

HI+

H+

I+

3P1/2 2[2]°5/2

71.5x103

71.4

71.3

71.2

71.1

71.0

70.9

70.8

Wav

enum

ber

/cm

-1

V1

+('=m+6)

Off-resonance Near-resonance

J'

9

8

76

0

.

.

.

H1

+('=1) J'

10

9

988

7

6

5

0

.

.

.

72.0x103

71.8

71.6

71.4

71.2

71.0

Wav

enum

ber

/cm

-1

O1

+('=0)

V1

+('=m+7)

k31('=1)

J'

10

9

8

7

6

5

.

.

0

J'

11

10

9

8

7

6

5

1

.

.

J'

0

9

11?

.

.

.

Off-resonance Near-resonance

0 1 2 3 4 5 6 7 8 90

0.2

0.4

0.6

0.8

1

1.2

ExpCal

J'

I(I+)/I(HI+)

Conclusions

• Courses will probably be finished at the end of next semester.

• If publications go as planned I will have 4-7 published papers early/mid 2014.

• Plenty of other research materials on the horizon.– CH3I. I2?

– Something overseas?

• Already new states have been found in HI as well as numerous, previously unreported, perturbation effects (whose publication is imminent).

• Even more new states have already been observed (which are reserved for the latter publication involving new states in HI).

Thank you!

Supplementary material

76x103

74

72

70

68

66

Wav

enum

ber /

cm-1

V1

+ (

6p

+ 3

(

5d

+ 3

m

m+1

m+3

m+2

m+4

m+5

m+6

m+7m+8m+9m+10

F

(1)

(2)

g (0+)

(0)

g (1±)

(1)

(0)

H

f

(0)(0)

(1)

E(0)

(1)

(2)j

(0)

Ginter et al.

This work

(0)O

(

4f

+

(0)I

78x103

76

74

72

70

68

66

Wav

enum

ber /

cm-1

(

5d

3

K(0)

k(0+)

k(1)

k(2)

(0)

(0)

(1)

(2)

(

6s

b(0+)

(3)

(

6p

3

D(0)

(1)

(2)

d(0+)

(0)

(

5d

N(0)

(

7s

m(1)

m(2)

(0)

(1)

(

7p

r(1)(0)

Ginter et al.

This work

(1)

Intensity ratios, I1Δ2 state

2 3 4 5 6 7 80

0.5

1

1.5

2

2.5

ExpCal

J'

I(I+)/I(HI+)

Bandwidths, I1Δ2 state