High-precision spectroscopic study of water and water containing van der Waals complexes

H2OLiquid wa e
(H2O)2(H2O)n
124
H2O-X
3
High-p ecision spec oscopic s udy o wa e and wa e con aining an de Waals complexes
A pe sonal jou ney
Thanks o he kind in i a ion
H2OLiquid wa e
CHEMISTRY
Physics
(H2O)2(H2O)n
(o he o he way a ound)
Rele an o as ochemis y, o ou a mosphe e
and o es molecula quan um models
124
Alex Huneycu and Richa d J. Saykally. "Building Solu ions one Molecule a a Time." Science 299.5611 (2003): 1329-1330.
H2O-X
3
High-p ecision spec oscopic s udy o wa e and wa e con aining an de Waals complexes
I0I
-ln(I/I0)
molecula spec um
L
spec o
me e
de ec o
How o measu e a spec um?
Pho on ene gies will be on he o de o
NIR 0.9 eV,1.4mm 86 kJ/mol, 7000 cm-1, 216 THz
MW 100 meV, 0.01 kJ/mol, 0.5 cm-1, 15 GHz
Leng h
o ligh -ma e in e ac ion
Abso p ion
coe icien
I0I
-ln(I/I0)
molecula spec um
Leng h
o ligh -ma e in e ac ion
L
spec o
me e
de ec o
Abso p ion
coe icien
Op ical spec oscopy
How o measu e a spec um?
Oscilla o 1 Oscilla o 2 Oscilla o 4
Oscilla o 3
-10000 -5000 0 5000 10000
- 0 / GHz
-10000 -5000 0 5000 10000
-
0
/ GHz
1
F ank Cozijn
Wim Ubachs Meïssa Diou
|𝐺⟩
|𝐸⟩
Dopple ee Lamb-dip
•Lamb-dip in Dopple
b oadened p o ile
•Fac o 1000 educ ion in
linewid h
•Sensi i i y o de ec he
p o ile
•Powe o bu n he hole
NICE
-
OHMS
Expe imen
om
VU
Addi ion o he op ical ca i y (ano he oscilla o )

1
NICE
-
OHMS
Expe imen
om
he VU
Simpli ied expe imen al se up scheme. ECDL : Ex e nal Ca i y Diode Lase , EOM : Elec o-Op ic Modula o ,
OFC : Op ical F equency Comb.
F ank Cozijn
Wim Ubachs Meïssa Diou
F om VU o UCLou ain
No embe 2024, VU’s Lase Lab
7
NICE-OHMS a UCLou ain
Two weeks la e in UCLou ain
F ank Coziijn A hémise Al man and Alexand Bogomolo
Jackson Labs Fu y GPS Disciplined Oscilla o
→ 10 à ≈ 1 𝑠 de moyennage.
𝛿𝜈 = 200 Hz @10
A equency comb locked o his oscilla o
The goal o ou s udy was o imp o e he accu acy o adio lines o wa e , which
ha e been lagged o adio as onomy by he In e na ional As onomical Union
h p://www.c a .eu/iau-lis -o -impo an -spec al-lines
Ligh sou ce:
Lase
M2M1
PZT De ec o :
Pho odiode
AOM
Expe imen al
se
-
up
: FANTASIO
Pulsed supe sonic expansion o o m
he molecula complexes
𝐿 ≈ 75 cm
𝑙 ≈ 2 cm
𝑅 ≈
99.9995 %
𝜏≈ 100 µ𝑠:
he ligh a els
~ 30 km inside
he ca i y (~1
km inside he
je ).
(H2O)2
2
Michel He man

(H2O)2
2
Suas-Da id, N.; Van le e en, T.; Földes, T.; Kassi, S.; Geo ges, R.; He man, M.
The wa e dime in es iga ed in he 2OH spec al ange using ca i y ing-down spec oscopy. The Jou nal o Physical Chemis y A 2015, 119 (39), 10022-10034.
18
Following hese s udies
Vog E, Simkó I, Császá AG, Kjae gaa d HG. Quan um Chemical In es iga ion o he Cold Wa e Dime Spec um in he Fi s OH-S e ching
O e one Region P o ides a New In e p e a ion. The Jou nal o Physical Chemis y A. 2023.
H2O − H2O
Calcula ed bands p o ile
« Could you eco d he
wa e dime spec a in
he egion o
he bound OH s e ch
( =2), which we e no
s udied in he 2 p e ious
expe imen al pape s »
N. Suas-Da id e
al., J. Chem. Phys.
A 119, 10022-
10034 (2020)
Emil
Vog
Hen ik G um
Kjae gaa d
19
H2O − H2O
N. Suas-Da id e
al., J. Chem. Phys.
A 119, 10022-
10034 (2020)
D . Alexande
Bogomolo
20
How does heo y pe o m?
H2O − H2O
N. Suas-Da id e
al., J. Chem. Phys.
A 119, 10022-
10034 (2020)
21

Calcula ed 12D
T = 20 K
(Zoomed and shi ed by 3 cm-1 )
Elusi e OHb-s e ching o e one, wa e dime
2𝜈
Fi s o e one OHb-s e ching is weak and band b oad
CCSD(T)-F12a/cc-pVDZ-F12 Emil
Vog
Hen ik G um
Kjae gaa d
Why o s udy he wa e -CO2 an de Waals complex?
H2O-X
3
Why o s udy he wa e -CO2 an de Waals complex?
In e media e s a e o p oduce ca bonic acid
𝐻2𝑂 𝑙 + 𝐶𝑂2𝑔→ 𝐻2𝐶𝑂3𝑎𝑞 ?? ?
Gene al chemis y class:
Fi s de ec ion in he gas phase o he ca bonic acid
in 2009
CHEMISTRY
MOLECULAR PHYSICS
T. Mo i e al., J. Chem. Phys., 130 (2009) 2043 How he in e molecula unneling « mo ion »
a ies wi h in amolecula ib a ional exci a ion?
ATMOSPHERE
Could CO2be s o ed
in cla h a es?
Q. Wang, J. Bowman, J. Chem. Phys,
147 (2017) 161714
Obse a ion o ib a ional shi o
CO2 3 band o igin in se e al objec s
ASTROPHYSICS
Objec s
Obse ed
ib a ional
Shi /cm-1
Ganymede +5.8
Callis o +5.2
Phoebe +3.7
Iape us +3.7
Hype ion +11.3
G. M. Chaban e al., Ica us, 187 (2007) 592
H2O-CO2
Single OD Exci a ion in D2O-CO2 measu ed in Calga y and analyzed in LLN
Asymme ic OD s e ching exci a ion
N. Moazzen Ahmadi
Ga ne , T.; Lauzin, C.; McKella , A.; Moazzen-Ahmadi, N. In a ed Spec a o he Wa e –CO2 Complex in he 4.3–3.6 μm Region and
De e mina ion o he G ound S a e Tunneling Spli ing o HDO–CO2. The Jou nal o Physical Chemis y A 2023, 127 (16), 3668-3674.
( 1’ ’2 ’3) ← ( 1’’ 2’’ 3’’)
(001)←(000)
(111)←(000)
(201)←(000)
Pa a nuclea spin
isome
Speci ically
b oadened

0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
11000
𝐸ℎ𝑐
[cm]
(𝜈,𝜈,𝜈) = (0,0,0)
↗ ib a ional exci a ion
(0,0,1)
(2,0,0)
(1,0,1)
(2,0,1)
𝑫𝟎
𝟐 𝐎𝐇 𝐬𝐭𝐫𝐞𝐭𝐜𝐡
𝟏 𝐎𝐃 𝐬𝐭𝐫𝐞𝐭𝐜𝐡
𝟑 𝐎𝐃 𝐬𝐭𝐫𝐞𝐭𝐜𝐡
(1, 1,1)
Ca bonic acid o ma ion
Mo i e al., J. Chem. Phys. 130, 20 (2009): 204308
2p
2s
1s11s2
O
o bi als
2b2
4a1
1b1
3a1
1b2
2a1
H
o bi als
H2O
o bi als
Ene gy
(1a1)2(2a1)2(1b2)2(3a1)2(1b1)2
Towa ds eac i e species!
Wha happens i one emo es an elec on?
D.A.
McQua ie
and J.D. Simon,
Physical
Chemis y
. A
Molecula
App oach
D.A.
McQua ie
and J.D. Simon,
Physical
Chemis y
. A
Molecula
App oach
Wha happens i one emo es an elec on?
2p
2s
1s11s2
O
o bi als
2b2
4a1
1b1
3a1
1b2
2a1
H
o bi als
H2O
o bi als
Ene gy
(1a1)2(2a1)2(1b2)2(3a1)2(1b1)1
Towa ds eac i e species!
Pho oelec on spec um o H2O (1968)
Woe ne ,H. J.;Me k , F. Handbook o High- esolu ion Spec oscopy 2011
C. R. B undle and D. W. Tu ne , P oceedings o he Royal Socie y o London Se ies a-Ma hema ical and Physical Sciences 307, 27
(1968)
I one zoom spec ally
1000x on he
band o igin

101700 101750 101800 101850 101900 101950 102000
0.0 0.5 1.0 1.5 2.0
Wa enumbe / cm
-1
Elec on o ion signal (a b. uni s)
D
2
O
D
2
O
D
2
O
D
2
O
D
2
O
D
2
O
D
2
O
D
2
OD
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
O
H
2
OH
2
O
HDO
HDO
HDO
HDO
HDO
HDO
HDO
HDOHDO
ZEKE and MATI spec oscopy
C. Lauzin, U. Jaco ella, F. Me k , Th eshold ioniza ion spec oscopy o H2O, HDO and D2O and low-
lying ib a ional le els o HDO+ and D
2
O+, Molecula Physics (2015) 1-7.
Fi s p ecise de e mina ion o he (adiaba ic) IP o HDO
Small inc ease o he pho oioniza ion c oss-sec ion
o HDO Vs D2O and H2O due o symme y easons
U. Jaco ella
(now in Pa is Saclay)
Pho o agmen a ion
Expe imen ally:
Two mass il e s/selec ions
and ion guiding op ics
(A-B)+->A++B
A+B+
You moni o A+o B+as a
unc ion o .
h
Ion sou ce Mass selec ion 1 Ligh -ma e
in e ac ion Mass selec ion 2
De ec ion
o he
p oduc s
H. A. Scwa z, M. Okumu a, Y. T. Lee
S a ga e se -up
Lens De lec ion
(2) Skimme
(6) Di e en ial pumping ube
(7) Lase ion beam in e ac ion
Pulsed nozzle &
elec on gun
90°
de lec o s
Bunching
uni
MCP de ec o
Lase
STARGATE = 3 pa s
1
P oduc ion o
ionic complexes
3
Ac ion spec oscopy :
pho o-dissocia ion
2
Mass selec ion
o he complexes
H2O+
H3O+
X+X-H2O+
X = A , N2O, CO2, …
X-H2O+
X2+
OH+
H2O+
H3O+
X+X-H2O+
X2-H2O+
X2 +
OH+
[X-H2O]+[X-H2O]* +
hυX + H2O+
Ac ion spec oscopy using pho o-dissocia ion
p ocesses in molecula sys ems
Spec oscopy o T ansien Anions and Radicals by
Ga ed and Accele a ed Time-o - ligh Expe imen
40
A -H2O+
5015 cm-1
6416 6435
6471
6347
6297
•Main ansi ions a 5015 cm-1 and 6420 cm-1 app ox.
A -H2O+
In eg a ed H2O+ agmen signal
Valida ion
D . Jo ey
F é eux
41
Pulsed OPO o ew cm-1 o esolu ion
100 X be e esolu ion.
Ro a ional s uc u e obse ed o he i s ime
o a molecula complex in he o e one ange.
Wa enumbe scale has o be p ope ly calib a ed.
A -H2O+
D . Jo ey
F é eux
Wha ’s nex ? Inc easing he esolu ion

(H2O)n
4
Can we make and s udy a d ople in he lab?
Wa e hep ame PR1 s uc u e
Pé ez C, Lobsige S, Sei e NA, Zaleski DP, Temelso B, Shields GC, e al. B oadband Fou ie ans o m o a ional
spec oscopy o s uc u e de e mina ion: The wa e hep ame . Chemical Physics Le e s. 2013;571:1-15.
This mon h imp o emen by a ac o 10 o he speed o measu emen s and au oma ion o he FANTASIO se -up (7/7,24/24)
Simon
Colignon
Pu e o a ional spec um o Wa e hep ame !
A Wha ’s nex ? Inc easing he numbe o a oms
CO2
Wha ’s nex ? Inc easing he numbe o a oms
Wha ’s nex ? Inc easing he p ecision
01/2026 we should be connec ed o a Hyd ogen mase e e ence….in he mean ime

ULE ca i y
PDH lock
Resul s
ECDL 1
ECDL 2
-10000 -5000 0 5000 10000
-
0
/ GHz
Bea ing equency 1
Bea ing equency 2
Ca i y 1
Ca i y 2
Compa ison o h ee « ul a »-s able oscilla o