PhD project overview - REMPI analyses of small, iodine containing molecules
description
Transcript of PhD project overview - REMPI analyses of small, iodine containing molecules
PhD project overview -REMPI analyses of small,
iodine containing moleculesHelgi 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 /e
V
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 /e
V
H I
1s
5s
5p
(n)
(b)
* (a)
(n)
HI
80x103
60
40
20
0
E [c
m-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)}.
Rel
ativ
e in
tens
ity /a
.u.
71.12x10371.1071.0871.0671.0471.0271.0070.98
Wavenumber /cm-1
k31('=1)d3
0('=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
Rel
ativ
e in
tens
ity /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)Q
05 4 ...
67
89
O012
m32('=0)
R2 3 4 5
S2 3 4 5
S2 3 4 V1
+('=m+6)
Q0123456
78
Q26
H+
I+
HI+
10
2P1/2 2[1]°3/2
2P1/2 2[0]°1/2
Rel
ativ
e in
tens
ity /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
O012
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
mm+1
m+3
m+2
m+4
m+5m+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