Download - PhD project overview - REMPI analyses of small, iodine containing molecules Helgi Rafn Hróðmarsson
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PhD project overview -REMPI analyses of small,
iodine containing molecules
Helgi Rafn Hróðmarsson
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Presentation overview
• Introduction• Courses• Project overview• Publications &
conferences• Timeline
• Experimental• Theory (diet)• Findings
– New states– State Interactions
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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.
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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)
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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"
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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
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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
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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
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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?
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Experimental setup
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The project
• From a chemist‘s point of view.– Molecular orbitals.– HOMO & LUMO
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-25
-20
-15
-10
E /
eV
H I
1s
5s
5p
(n)
(b)
* (a)
(n)
HI
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The project
• From a physicist‘s point of view.
• Hamiltonians• Harmonic oscillator• Rigid Rotor
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-25
-20
-15
-10
E /
eV
H I
1s
5s
5p
(n)
(b)
* (a)
(n)
HI
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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
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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)}.
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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
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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
:
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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.
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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
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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
.
.
.
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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
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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+)
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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).
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Thank you!
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Supplementary material
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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
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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)
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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+)
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Bandwidths, I1Δ2 state
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