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

H2OLiquid water (H2O)2(H2O)n 124 H2O-X 3 High-precision spectroscopic study of water and water containing van der Waals complexes A personal journey Thanks for the kind invitation H2OLiquid water CHEMISTRY Physics (H2O)2(H2O)n (or the other way around) Relevant for astrochemistry, for our atmosphere and to test molecular quantum models 124 Alex Huneycutt and Richard J. Saykally. "Building Solutions one Molecule at a Time." Science 299.5611 (2003): 1329-1330. H2O-X 3 High-precision spectroscopic study of water and water containing van der Waals complexes I0I -ln(I/I0) molecular spectrum L spectro meter detector How to measure a spectrum? Photon energies will be on the order of 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 Length of light-matter interaction Absorption coefficient I0I -ln(I/I0) molecular spectrum Length of light-matter interaction L spectro meter detector Absorption coefficient Optical spectroscopy How to measure a spectrum? Oscillator 1 Oscillator 2 Oscillator 4 Oscillator 3 -10000 -5000 0 5000 10000 f - f0 / GHz -10000 -5000 0 5000 10000 f - f 0 / GHz 1 Frank Cozijn Wim Ubachs Meïssa Diouf |𝐺⟩ |𝐸⟩ Doppler free Lamb-dip •Lamb-dip in Doppler broadened profile •Factor 1000 reduction in linewidth •Sensitivity to detect the profile •Power to burn the hole NICE - OHMS Experiment from VU Addition of the optical cavity (another oscillator) 1 NICE - OHMS Experiment from the VU Simplified experimental setup scheme. ECDL : External Cavity Diode Laser, EOM : Electro-Optic Modulator, OFC : Optical Frequency Comb. Frank Cozijn Wim Ubachs Meïssa Diouf From VU to UCLouvain November 2024, VU’s LaserLab 7 NICE-OHMS at UCLouvain Two weeks later in UCLouvain Frank Coziijn Arthémise Altman and Alexandr Bogomolov Jackson Labs Fury GPS Disciplined Oscillator → 10 à ≈ 1 𝑠 de moyennage. 𝛿𝜈 = 200 Hz @10 A frequency comb locked to this oscillator The goal of our study was to improve the accuracy of radio lines of water, which have been flagged for radio astronomy by the International Astronomical Union http://www.craf.eu/iau-list-of-important-spectral-lines Light source: Laser M2M1 PZT Detector: Photodiode AOM Experimental set - up : FANTASIO Pulsed supersonic expansion to form the molecular complexes 𝐿 ≈ 75 cm 𝑙 ≈ 2 cm 𝑅 ≈ 99.9995 % 𝜏≈ 100 µ𝑠: the light travels ~ 30 km inside the cavity (~1 km inside the jet). (H2O)2 2 Michel Herman (H2O)2 2 Suas-David, N.; Vanfleteren, T.; Földes, T.; Kassi, S.; Georges, R.; Herman, M. The water dimer investigated in the 2OH spectral range using cavity ring-down spectroscopy. The Journal of Physical Chemistry A 2015, 119 (39), 10022-10034. 18 Following these studies Vogt E, Simkó I, Császár AG, Kjaergaard HG. Quantum Chemical Investigation of the Cold Water Dimer Spectrum in the First OH-Stretching Overtone Region Provides a New Interpretation. The Journal of Physical Chemistry A. 2023. H2O − H2O Calculated bands profile « Could you record the water dimer spectra in the region of the bound OH stretch (v=2), which were not studied in the 2 previous experimental papers » N. Suas-David et al., J. Chem. Phys. A 119, 1002210034 (2020) Emil Vogt Henrik Grum Kjaergaard 19 H2O − H2O N. Suas-David et al., J. Chem. Phys. A 119, 1002210034 (2020) Dr. Alexander Bogomolov 20 How does theory perform? H2O − H2O N. Suas-David et al., J. Chem. Phys. A 119, 1002210034 (2020) 21 Calculated 12D T = 20 K (Zoomed and shifted by 3 cm-1 ) Elusive OHb-stretching overtone, water dimer 2𝜈 First overtone OHb-stretching is weak and band broad CCSD(T)-F12a/cc-pVDZ-F12 Emil Vogt Henrik Grum Kjaergaard Why to study the water-CO2van der Waals complex? H2O-X 3 Why to study the water-CO2van der Waals complex? Intermediate state to produce carbonic acid 𝐻2𝑂 𝑙 + 𝐶𝑂2𝑔→ 𝐻2𝐶𝑂3𝑎𝑞 ?? ? General chemistry class: First detection in the gas phase of the carbonic acid in 2009 CHEMISTRY MOLECULAR PHYSICS T. Mori et al., J. Chem. Phys., 130 (2009) 2043 How the intermolecular tunneling « motion » varies with intramolecular vibrational excitation? ATMOSPHERE Could CO2be stored in clathrates? Q. Wang, J. Bowman, J. Chem. Phys, 147 (2017) 161714 Observation of vibrational shift of CO2 3 band origin in several objects ASTROPHYSICS Objects Observed vibrational Shift/cm-1 Ganymede +5.8 Callisto +5.2 Phoebe +3.7 Iapetus +3.7 Hyperion +11.3 G. M. Chaban et al., Icarus, 187 (2007) 592 H2O-CO2 Single OD Excitation in D2O-CO2 measured in Calgary and analyzed in LLN Asymmetric OD stretching excitation N. Moazzen Ahmadi Gartner, T.; Lauzin, C.; McKellar, A.; Moazzen-Ahmadi, N. Infrared Spectra of the Water–CO2 Complex in the 4.3–3.6 μm Region and Determination of the Ground State Tunneling Splitting for HDO–CO2. The Journal of Physical Chemistry A 2023, 127 (16), 3668-3674. (v1’v’2v’3) ← (v1’’ v2’’ v3’’) (001)←(000) (111)←(000) (201)←(000) Para nuclear spin isomer Specifically broadened 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000 𝐸ℎ𝑐 [cm] (𝜈,𝜈,𝜈) = (0,0,0) ↗vibrational excitation (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) Carbonic acid formation Mori et al., J. Chem. Phys. 130, 20 (2009): 204308 2p 2s 1s11s2 O orbitals 2b2 4a1 1b1 3a1 1b2 2a1 H orbitals H2O orbitals Energy (1a1)2(2a1)2(1b2)2(3a1)2(1b1)2 Towards reactive species! What happens if one removes an electron? D.A. McQuarrie and J.D. Simon, Physical Chemistry . A Molecular Approach D.A. McQuarrie and J.D. Simon, Physical Chemistry . A Molecular Approach What happens if one removes an electron? 2p 2s 1s11s2 O orbitals 2b2 4a1 1b1 3a1 1b2 2a1 H orbitals H2O orbitals Energy (1a1)2(2a1)2(1b2)2(3a1)2(1b1)1 Towards reactive species! Photoelectron spectrum of H2O (1968) Woerner,H. J.;Merkt, F. Handbook of High-resolution Spectroscopy 2011 C. R. Brundle and D. W. Turner, Proceedings of the Royal Society of London Series a-Mathematical and Physical Sciences 307, 27 (1968) If one zoom spectrally 1000x on the band origin 101700 101750 101800 101850 101900 101950 102000 0.0 0.5 1.0 1.5 2.0 Wavenumber / cm -1 Electron or ion signal (arb. units) 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 spectroscopy C. Lauzin, U. Jacovella, F. Merkt, Threshold ionization spectroscopy of H2O, HDO and D2O and lowlying vibrational levels of HDO+ and D 2 O+, Molecular Physics (2015) 1-7. First precise determination of the (adiabatic) IP of HDO Small increase of the photoionization cross-section of HDO Vs D2O and H2O due to symmetry reasons U. Jacovella (now in Paris Saclay) Photofragmentation Experimentally: Two mass filters/selections and ion guiding optics (A-B)+->A++B A+B+ You monitor A+or B+as a function of . h Ion source Mass selection 1 Light-matter interaction Mass selection 2 Detection of the products H. A. Scwartz, M. Okumura, Y. T. Lee Stargate set-up Lens Deflection (2) Skimmer (6) Differential pumping tube (7) Laser ion beam interaction Pulsed nozzle & electron gun 90° deflectors Bunching unit MCP detector Laser STARGATE = 3 parts 1 Production of ionic complexes 3 Action spectroscopy : photo-dissociation 2 Mass selection of the complexes H2O+ H3O+ X+X-H2O+ X = Ar, N2O, CO2, … X-H2O+ X2+ OH+ H2O+ H3O+ X+X-H2O+ X2-H2O+ X2 + OH+ [X-H2O]+[X-H2O]* + hυX + H2O+ Action spectroscopy using photo-dissociation processes in molecular systems Spectroscopy of Transient Anions and Radicals by Gated and Accelerated Time-of-flight Experiment 40 Ar-H2O+ 5015 cm-1 6416 6435 6471 6347 6297 •Main transitions at 5015 cm-1 and 6420 cm-1 approx. Ar-H2O+ Integrated H2O+fragment signal Validation Dr. Joffrey Fréreux 41 Pulsed OPO of few cm-1 of resolution 100 X better resolution. Rotational structure observed for the first time for a molecular complex in the overtone range. Wavenumber scale has to be properly calibrated. Ar-H2O+ Dr. Joffrey Fréreux What’s next? Increasing the resolution (H2O)n 4 Can we make and study a droplet in the lab? Water heptamer PR1 structure Pérez C, Lobsiger S, Seifert NA, Zaleski DP, Temelso B, Shields GC, et al. Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer. Chemical Physics Letters. 2013;571:1-15. This month improvement by a factor 10 of the speed of measurements and automation of the FANTASIO set-up (7/7,24/24) Simon Colignon Pure rotational spectrum of Water heptamer! Ar What’s next? Increasing the number of atoms CO2 What’s next? Increasing the number of atoms What’s next? Increasing the precision 01/2026 we should be connected to a Hydrogen maser reference….in the meantime ULE cavity PDH lock Results ECDL 1 ECDL 2 -10000 -5000 0 5000 10000 f - f 0 / GHz Beating frequency 1 Beating frequency 2 Cavity 1 Cavity 2 Comparison of three « ultra »-stable oscillator