Energy dependence; Energy ranges; Interstellar medias; Monotonic energy; Monotonics; Non-adiabatic; Product channel; Quantum dynamics; Ultraviolet photodissociation; Vacuum ultraviolets; Physics and Astronomy (all); Physical and Theoretical Chemistry
Abstract :
[en] Vacuum ultraviolet (VUV) photodissociation of N2 molecules is a source of reactive N atoms in the interstellar medium. In the energy range of VUV optical excitation of N2, the N-N triple bond cleavage leads to three types of atoms: ground-state N(4S) and excited-state N(2P) and N(2D). The latter is the highest reactive and it is believed to be the primary participant in reactions with hydrocarbons in Titan's atmosphere. Experimental studies have observed a non-monotonic energy dependence and non-statistical character of the photodissociation of N2. This implies different dissociation pathways and final atomic products for different wavelength regions in the sunlight spectrum. We here apply ab initio quantum chemical and nonadiabatic quantum dynamical techniques to follow the path of an electronic state from the excitation of a particular singlet 1Σ+u and 1Πu vibronic level of N2 to its dissociation into different atomic products. We simulate dynamics for two isotopomers of the nitrogen molecule, 14N2 and 14N15N for which experimental data on the branching are available. Our computations capture the non-monotonic energy dependence of the photodissociation branching ratios in the energy range 108 000-116 000 cm-1. Tracing the quantum dynamics in a bunch of electronic states enables us to identify the key components that determine the efficacy of singlet to triplet population transfer and therefore predissociation lifetimes and branching ratios for different energy regions.
Disciplines :
Chemistry
Author, co-author :
Gelfand, Natalia ; The Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel. natalia.gelfand@mail.huji.ac.il
Komarova, Ksenia ; The Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel. natalia.gelfand@mail.huji.ac.il
Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique ; The Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel. natalia.gelfand@mail.huji.ac.il
Levine, R D ; The Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel. natalia.gelfand@mail.huji.ac.il ; Department of Molecular and Medical Pharmacology, David Geffen School of Medicine and Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA
Language :
English
Title :
Nonadiabatic quantum dynamics explores non-monotonic photodissociation branching of N2 into the N(4S) + N(2D) and N(4S) + N(2P) product channels.
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] BSF - United States-Israel Binational Science Foundation [IL]
Funding text :
The authors acknowledge financial support of the US–Israel NSF–BSF grant no. 2019722. F. R. acknowledges the support of the Fonds National de la Recherche (F. R. S.-FNRS, Belgium), grant no. T0205.20 and COST action ATTOCHEM (CA18222).
McGuire B. A. Census of Interstellar, Circumstellar, Extragalactic, Protoplanetary Disk, and Exoplanetary Molecules Astrophys. J., Suppl. Ser. 2021 2022 259 30
Cami J. Bernard-Salas J. Peeters E. Malek S. E. Detection of C60 and C70 in a Young Planetary Planetary Nebula Science 2010 329 1180 1182 10.1126/science.1192035 20651118
Williams D. A. and Cecchi-Pestellini C., Astrochemistry: Chemistry in Interstellar and Circumstellar Space, Royal Society of Chemistry, 1st edn, 2023, p. 248
Bergin E. A. Langer W. D. Goldsmith P. F. Gas-phase chemistry in dense interstellar clouds including grain surface molecular depletion and desorption Astrophys. J. 1995 441 222 243 10.1086/175351
Gonzalez C. Schlegel H. B. Atmospheric Chemistry of Titan: Ab Initio Study of the Reaction between Nitrogen Atoms and Methyl Radicals J. Am. Chem. Soc. 1992 114 9118 9122 10.1021/ja00049a052
McKellar A. Evidence for the molecular origin of some hitherto unidentified interstellar lines Astron. Soc. Pac. 1940 52 187 192 10.1086/125159
Adams W. S. Some Results with the COUDÉ Spectrograph of the Mount Wilson Observatory Astrophys. J. 1941 93 11 10.1086/144237
Jefferts K. B. Penzias A. A. Wilson R. W. Observation of the CN Radical in the Orion Nebula and W51 Astrophys. J. 1970 161 87 89 10.1086/180576
Gallagher J. J. Johnson C. M. Uncoupling Effects in the Microwave Spectrum of Nitric Oxide Phys. Rev. 1956 103 1727 1737 10.1103/PhysRev.103.1727
Liszt H. S. Turner B. E. Microwave Detection of Interstellar NO Astrophys. J. 1978 224 73 76 10.1086/182762
Cernicharo J. Velilla-Prieto L. Agúndez M. Pardo J. R. Fonfría J. P. Quintana-Lacaci G. Cabezas C. Bermúdez C. Guélin M. Discovery of the first Ca-bearing molecule in space: CaNC Astron. Astrophys. 2019 627 L4 10.1051/0004-6361/201936040 31327871
Johnson D. R. Lovas F. J. Microwave Detection of the Molecular Transient Methyleneimine (CH2 = NH) Chem. Phys. Lett. 1972 15 65 68 10.1016/0009-2614(72)87017-9
Godfrey P. D. Brown R. D. Robinson B. J. Discovery S. M. W. of Interstellar Methanimine (Formaldimine) Astrophys. Lett. 1973 13 119 121
Belloche A. Garrod R. T. Müller H. S. P. Menten K. M. Medvedev I. Thomas J. Kisiel Z. Re-exploring Molecular Complexity with ALMA (ReMoCA): Interstellar detection of urea Astron. Astrophys. 2019 628 A10 10.1051/0004-6361/201935428
Vuitton V. Yelle R. V. Anicich V. G. The Nitrogen Chemistry of Titan's Upper Atmosphere Revealed Astrophys. J. 2006 647 175 178 10.1086/507467
He C. Smith M. A. Identification of nitrogenous organic species in Titan aerosols analogs: Nitrogen fixation routes in early atmospheres Icarus 2013 226 33 40 10.1016/j.icarus.2013.05.013
He C. Smith M. A. Identification of nitrogenous organic species in Titan aerosols analogs: Implication for prebiotic chemistry on Titan and early Earth Icarus 2014 238 86 92 10.1016/j.icarus.2014.05.012
Vuitton V. Yelle R. V. Klippenstein S. J. Hörst S. M. Lavvas P. Simulating the density of organic species in the atmosphere of Titan with a coupled ion-neutral photochemical model Icarus 2019 324 120 197 10.1016/j.icarus.2018.06.013
Cui J. Yelle R. V. Vuitton V. Waite J. H. Kasprzak W. T. Gell D. A. Niemann H. B. Müller-Wodarg I. C. F. Borggren N. Fletcher G. G. Patrick E. L. Raaen E. Magee B. A. Analysis of Titan's neutral upper atmosphere from Cassini Ion Neutral Mass Spectrometer measurements Icarus 2009 200 581 615 10.1016/j.icarus.2008.12.005
Balucani N. Skouteris D. Leonori F. Petrucci R. Hamberg M. Geppert W. D. Casavecchia P. Rosi M. Combined crossed beam and theoretical studies of the N(2D) + C2H4 reaction and implications for atmospheric models of titan J. Phys. Chem. A 2012 116 10467 10479 10.1021/jp3072316 23016665
Balucani N. and Skouteris D., in Prebiotic Photochemistry: From Urey-Miller-like Experiments to Recent Findings, ed. F. Saija and G. Cassone, The Royal Society of Chemistry, 1st edn, 2021, pp. 37-59
He C. Serigano J. Hörst S. M. Radke M. Sebree J. A. Titan Atmospheric Chemistry Revealed by Low-Temperature N2-CH4Plasma Discharge Experiments ACS Earth Sp. Chem. 2022 6 2295 2304 10.1021/acsearthspacechem.2c00164
Brown R. Winkler C. A. The Chemical Behavior of Active Nitrogen Angew. Chem., Int. Ed. Engl. 1970 9 181 196 10.1002/anie.197001811
Herron J. T. Evaluated Chemical Kinetics Data for Reactions of N(2D), N(2P), and N2(A3Σu +) in the Gas Phase J. Phys. Chem. Ref. Data 1999 28 1453 1483 10.1063/1.556043
Suzuki T. Shihira Y. Sato T. Umemoto H. Tsunashima S. Reactions of N(22D) and N(22P) with H2 and D2 J. Chem. Soc., Faraday Trans. 1994 89 995 999 10.1039/FT9938900995
Donovan R. J. Husain D. Recent advances in the chemistry of electronically excited atoms Chem. Rev. 1970 70 489 516 10.1021/cr60266a003
Schofield K. Critically evaluated rate constants for gaseous reactions of several electronically excited species J. Phys. Chem. Ref. Data 1979 8 723 798 10.1063/1.555606
Vanuzzo G. Marchione D. Mancini L. Liang P. Pannacci G. Recio P. Tan Y. Rosi M. Skouteris D. Casavecchia P. Balucani N. The N(2D) + CH2CHCN (Vinyl Cyanide) Reaction: A Combined Crossed Molecular Beam and Theoretical Study and Implications for the Atmosphere of Titan J. Phys. Chem. A 2022 126 6110 6123 10.1021/acs.jpca.2c04263 36053010
Mancini L. Vanuzzo G. Marchione D. Pannacci G. Liang P. Recio P. Rosi M. Skouteris D. Casavecchia P. Balucani N. The Reaction N(2D) + CH3CCH (Methylacetylene): A Combined Crossed Molecular Beams and Theoretical Investigation and Implications for the Atmosphere of Titan J. Phys. Chem. A 2021 125 8846 8859 10.1021/acs.jpca.1c06537 34609869
Recio P. Marchione D. Caracciolo A. Murray V. J. Mancini L. Rosi M. Casavecchia P. Balucani N. A crossed molecular beam investigation of the N(2D) + pyridine reaction and implications for prebiotic chemistry Chem. Phys. Lett. 2021 779 138852 10.1016/j.cplett.2021.138852
Hickson K. M. Bray C. Loison J. C. Dobrijevic M. A kinetic study of the N(2D) + C2H4reaction at low temperature Phys. Chem. Chem. Phys. 2020 22 14026 14035 10.1039/D0CP02083D 32558865
Mancini L. Rosi M. Skouteris D. Vanuzzo G. Pannacci G. Casavecchia P. Balucani N. A computational characterization of the reaction mechanisms for the reactions N(2D) + CH3CN and HC3N and implications for the nitrogen-rich organic chemistry of Titan Comput. Theor. Chem. 2023 1229 114341 10.1016/j.comptc.2023.114341
Geiger J. Schröder B. Intensity perturbations due to configuration interaction observed in the electron energy-loss spectrum of N2 J. Chem. Phys. 1969 50 107 119 10.1063/1.1670870
Liu M. Jiang P. Cheng M. Gao H. Vacuum ultraviolet photoexcitation and photofragment spectroscopic studies of 14N15N between 109000 and 117500 cm−1 J. Chem. Phys. 2021 155 234305 10.1063/5.0072604 34937384
Spelsberg D. Meyer W. Dipole-allowed excited states of N2: Potential energy curves, vibrational analysis, and absorption intensities J. Chem. Phys. 2001 115 6438 6449 10.1063/1.1400139
Zipf E. C. McLaughlin R. W. On the dissociation of nitrogen by electron impact and by EUV photo-absorption Planet. Sp. Sci. 1977 26 449 462 10.1016/0032-0633(78)90066-1
Helm H. Cosby P. C. Product branching in predissociation of the e 1Πu, e′1Σu +, and b′ 1Σu+ states of N2 J. Chem. Phys. 1989 90 4208 4215 10.1063/1.455777
Walter C. W. Cosby P. C. Helm H. N(4S0), N(2D0), and N(2P0) yields in predissociation of excited singlet states of N2 J. Chem. Phys. 1993 99 3553 3561 10.1063/1.466152
Walter C. W. Cosby P. C. Helm H. Predissociation quantum yields of singlet nitrogen Phys. Rev. A 1994 50 2930 2936 10.1103/PhysRevA.50.2930 9911235
Chakraborty S. Muskatel B. H. Jackson T. L. Ahmed M. Levine R. D. Thiemens M. H. Cerling T. E. Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data Proc. Natl. Acad. Sci. U. S. A. 2014 111 14704 14709 10.1073/pnas.1410440111 25267643
Chakraborty S. Jackson T. L. Rude B. Ahmed M. Thiemens M. H. Nitrogen isotopic fractionations in the low temperature (80 K) vacuum ultraviolet photodissociation of N2 J. Chem. Phys. 2016 145 114302 10.1063/1.4962447
Song Y. Gao H. Chang Y. C. Hammouténe D. Ndome H. Hochlaf M. Jackson W. M. Ng C. Y. Quantum-State Dependence of Product Branching Ratios in Vacuum Ultraviolet Photodissociation of N2 Astrophys. J. 2016 819 23 10.3847/0004-637X/819/1/23
Liu M. Jiang P. Lu L. Yin T. Ma L. Cheng M. Yin Q. Gao H. Strong Isotope-dependent Photodissociation Branching Ratios of N2 and Their Potential Implications for the 14N/15N Isotope Fractionation in Titan's Atmosphere Astrophys. J. 2021 923 196 10.3847/1538-4357/ac2f97
Jiang P. Lu L. Liu M. Gao H. Multi-channel photodissociation dynamics of 14N2 in its b′ 1Σ + u(ν = 20) state Phys. Chem. Chem. Phys. 2022 24 11544 11551 10.1039/D2CP01148D 35506911
Lu L. Jiang P. Gao H. Accurate measurements of the bond dissociation energies of 14N2, 14N15N and 15N2 Fundam. Res. 2022 https://dx.doi.org/10.1016/j.fmre.2022.08.003
Sharpe S. W. Johnson P. M. Triplet Rydberg states in molecular nitrogen J. Chem. Phys. 1986 85 4943 4948 10.1063/1.451732
Lewis B. R. Heays A. N. Gibson S. T. Lefebvre-Brion H. Lefebvre R. A coupled-channel model of the 3Πu states of N2: Structure and interactions of the 3sσgF 3 3Πu and 3pπuG3 3Πu Rydberg states J. Chem. Phys. 2008 129 164306 10.1063/1.2990656 19045265
Minaev B. Norman P. Jonsson D. Ågren H. Response theory calculations of singlet-triplet transitions in molecular nitrogen Chem. Phys. 1995 190 11 29 10.1016/0301-0104(94)00321-Z
Qin Z. Zhao J. Liu L. Radiative transition probabilities between low-lying electronic states of N2 Mol. Phys. 2019 117 2418 2433 10.1080/00268976.2018.1562579
Minaev B. F. Panchenko O. O. Minaeva V. A. Ågren H. Triplet state harvesting and search for forbidden transition intensity in the nitrogen molecule Front. Chem. 2022 10 1 10
Minaev B. Da Silva R. S. Panchenko O. Ågren H. Prediction of new spin-forbidden transitions in the N2 molecule - The electric dipole A′5Σg + → A3Σu+ and magnetic dipole a′1Σu-← A3Σu+ transitions J. Chem. Phys. 2023 158 084304 10.1063/5.0136465 36859101
Gilmore F. R. Potential energy curves for N2, NO, O2 and corresponding ions J. Quant. Spectrosc. Radiat. Transf. 1965 5 369 389 10.1016/0022-4073(65)90072-5
Lefebvre-Brion H. Moser C. M. Calculation of Rydberg levels in the nitrogen molecule J. Chem. Phys. 1965 43 1394 1399 10.1063/1.1696931
Little D. A. Tennyson J. An ab initio study of singlet and triplet Rydberg states of N2 J. Phys. B: At., Mol. Opt. Phys. 2013 46 145102 10.1088/0953-4075/46/14/145102
Ermler W. C. Clark J. P. Mulliken R. S. Ab initio calculations of potential energy curves and transition moments of 1Σg+ and 1Σ u+ states of N2 J. Chem. Phys. 1987 86 370 375 10.1063/1.452573
Hochlaf M. Ndome H. Hammoutne D. Quintet electronic states of N2 J. Chem. Phys. 2010 132 104310 10.1063/1.3359000 20232963
Hochlaf M. Ndome H. Hammoutène D. Vervloet M. Valence-Rydberg electronic states of N2: Spectroscopy and spin-orbit couplings J. Phys. B: At., Mol. Opt. Phys. 2010 43 245101 10.1088/0953-4075/43/24/245101
Adamson S. O. Kuverova V. V. Ozerov G. K. Golubkov G. V. Nabiev S. S. Golubkov M. G. Ab Initio Calculation of the Lowest Singlet and Triplet Excited States of the N2 Molecule Russ. J. Phys. Chem. B 2018 12 620 631 10.1134/S1990793118040024
Bhattacharya D. Shamasundar K. R. Emmanouilidou A. Potential Energy Curves of Molecular Nitrogen for Singly and Doubly Ionized States with Core and Valence Holes J. Phys. Chem. A 2021 125 7778 7787 10.1021/acs.jpca.1c04613 34477371
Stahel D. Leoni M. Dressler K. Nonadiabatic representations of the 1Σu+ and 1Πu states of the N2 molecule J. Chem. Phys. 1983 79 2541 2558 10.1063/1.446166
Curchod B. F. E. Martínez T. J. Chem. Rev. 2018 118 3305 3336 10.1021/acs.chemrev.7b00423 29465231
Schlegel H. B. Ab Initio Direct Dynamics Acc. Chem. Res. 2021 54 3749 3759 10.1021/acs.accounts.1c00390 34590487
Nisoli M. Decleva P. Calegari F. Palacios A. Martín F. Attosecond Electron Dynamics in Molecules Chem. Rev. 2017 117 10760 10825 10.1021/acs.chemrev.6b00453 28488433
Lassmann Y. Hollas D. Curchod B. F. E. Extending the Applicability of the Multiple-Spawning Framework for Nonadiabatic Molecular Dynamics J. Phys. Chem. Lett. 2022 13 12011 12018 10.1021/acs.jpclett.2c03295 36541684
Gelfand N. Komarova K. Remacle F. Levine R. D. Nonadiabatic dynamics in a forest of coupled states: Electronic state branching in the VUV photodissociation of N2 J. Chem. Phys. 2023 158 164302 10.1063/5.0148798 37102444
Trabattoni A. Klinker M. González-Vázquez J. Liu C. Sansone G. Linguerri R. Hochlaf M. Klei J. Vrakking M. J. J. Martín F. Nisoli M. Calegari F. Mapping the dissociative ionization dynamics of molecular nitrogen with attosecond time resolution Phys. Rev. X 2015 5 041053
Klinker M. Marante C. Argenti L. González-Vázquez J. Martín F. Electron Correlation in the Ionization Continuum of Molecules: Photoionization of N2 in the Vicinity of the Hopfield Series of Autoionizing States J. Phys. Chem. Lett. 2018 9 756 762 10.1021/acs.jpclett.7b03220 29364687
Ayari T. Desouter-Lecomte M. Linguerri R. Garcia G. A. Nahon L. Ben Houria A. Ghalila H. Ben Said R. Hochlaf M. State-to-state dissociative photoionization of molecular nitrogen: the full story Adv. Phys. X 2020 5 1831955 https://dx.doi.org/10.1080/23746149.2020.1831955
Muskatel B. H. Remacle F. Levine R. D. AttoPhotoChemistry. Probing ultrafast electron dynamics by the induced nuclear motion: The prompt and delayed predissociation of N2 Chem. Phys. Lett. 2014 601 45 48 10.1016/j.cplett.2014.03.031
Ajay J. Šmydke J. Remacle F. Levine R. D. Probing in Space and Time the Nuclear Motion Driven by Nonequilibrium Electronic Dynamics in Ultrafast Pumped N2 J. Phys. Chem. A 2016 120 3335 3342 10.1021/acs.jpca.6b00165 26937745
Ajay J. S. Komarova K. G. Remacle F. Levine R. D. Time-dependent view of an isotope effect in electron-nuclear nonequilibrium dynamics with applications to N2 Proc. Natl. Acad. Sci. U. S. A. 2018 115 5890 5895 10.1073/pnas.1804455115 29784776
Komarova K. G. Remacle F. Levine R. D. Time resolved mechanism of the isotope selectivity in the ultrafast light induced dissociation in N2 J. Chem. Phys. 2019 151 114308 10.1063/1.5118990 31542039
Gelfand N. Komarova K. Remacle F. Levine R. D. On the energy-specific photodissociation pathways of 14N2 and 14N15N isotopomers to N atoms of different reactivity: a quantum dynamical perspective Astrophys. J. 2023 948 58 10.3847/1538-4357/acbef8
Lefebvre-Brion H. and Field R. W., The Spectra and Dynamics of Diatomic Molecules, Elsevier, Amsterdam, 2004
Werner H. J. Knowles P. J. A second order multiconfiguration SCF procedure with optimum convergence J. Chem. Phys. 1985 82 5053 5063 10.1063/1.448627
Knowles P. J. Werner H. J. An efficient second-order MC SCF method for long configuration expansions Chem. Phys. Lett. 1985 115 259 267 10.1016/0009-2614(85)80025-7
Guberman S. L. Spectroscopy above the ionization threshold: Dissociative recombination of the ground vibrational level of N2 J. Chem. Phys. 2012 137 074309 10.1063/1.4739472 22920122
Werner H. J. Knowles P. J. Knizia G. Manby F. R. Schütz M. Molpro: A general-purpose quantum chemistry program package Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2012 2 242 253
Werner H. J. Knowles P. J. Manby F. R. Black J. A. Doll K. Heßelmann A. Kats D. Köhn A. Korona T. Kreplin D. A. Ma Q. Miller T. F. Mitrushchenkov A. Peterson K. A. Polyak I. Rauhut G. Sibaev M. The Molpro quantum chemistry package J. Chem. Phys. 2020 152 144107 10.1063/5.0005081 32295355
Ajay J. S., Komarova K. G., Van Den Wildenberg S., Remacle F. and Levine R. D., in Theoretical and Computational Chemistry Series, ed. M. J. J. Vrakking and F. Lepine, The Royal Society of Chemistry, Cambridge, 2018, pp. 308-347
Fornberg B. Generation of Finite Difference Formulas on Arbitrarily Spaced Grids Math. Comput. 1988 51 699 10.1090/S0025-5718-1988-0935077-0
Li X. Heays A. N. Visser R. Ubachs W. Lewis B. R. Gibson S. T. Van Dishoeck E. F. Photodissociation of interstellar N2 Astron. Astrophys. 2013 555 A14 10.1051/0004-6361/201220625
Gelfand N. Remacle F. Levine R. D. Recombination of N Atoms in a Manifold of Electronic States Simulated by Time-Reversed Nonadiabatic Photodissociation Dynamics of N2 J. Phys. Chem. Lett. 2023 14 4625 4630 10.1021/acs.jpclett.3c00666 37166125
Gelfand N. Komarova K. Remacle F. Levine R. D. Photodissociation via weak intersystem crossing: Incoherent versus coherent excited-state nonadiabatic dynamics in N2 Phys. Rev. A 2023 108 053116 10.1103/PhysRevA.108.053116
