Abstract
The dissociation of the simplest Criegee intermediate (H\(_2\)COO) into formaldehyde (H\(_2\)CO) and oxygen atom (O) is very important in the atmospheric chemistry. In this study, we investigate the photodissociation of the O–O bond of H\(_2\)COO by simulating the dynamics of the process on the fitted multiconfigurational adiabatic potential energy surfaces (PESs). Tully’s fewest-switches surface hopping (FSSH) method is used for the simulation. The FSSH trajectories are initiated on the lowest optically-bright singlet excited state (\(S_2\)) and propagated along the O–O coordinate. Some of the trajectories end up on energetically lower PESs as a result of radiationless transfer through conical intersections. However, all the trajectories lead to O–O bond dissociation via one of the two channels. The simulation results demonstrate that the restricted O–O motion dissociates H\(_2\)COO into singlet fragments via the lower energy channel. The coupling of electronic states along O–O may account for this.
Graphical abstract
The photodissociation of simplest Criegee intermediate (H2COO) into formaldehyde (H2CO) and oxygen (O) was studied using Tully's fewest-switches surface hopping (FSSH). The simulation results demonstrate that the restricted O–O motion dissociates into singlet fragments via the lower energy channel.
Similar content being viewed by others
References
Criegee R 1975 Mechanism of ozonolysis Angew. Chem. Int. Ed. 14 745
Johnson D and Marston G 2008 The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere Chem. Soc. Rev. 37 699
Zhong J, Kumar M, Francisco J S and Zeng X C 2018 Insight into chemistry on cloud/aerosol water surfaces Acc. Chem. Res. 51 1229
Wei W-M, Hong S, Fang W-J, Zheng R-H and Qin Y-D 2019 Formation of oh radicals from the simplest Criegee intermediate CH\(_{2}\)OO and water Theor. Chem. Acc. 138 13
Kumar M and Francisco J S 2019 Elucidating the molecular mechanisms of Criegee-amine chemistry in the gas phase and aqueous surface environments Chem. Sci. 10 743
Taatjes C A, Shallcross D E and Percival C J 2014 Research frontiers in the chemistry of Criegee intermediates and tropospheric ozonolysis Phys. Chem. Chem. Phys. 16 1704
Mauldin R L 3rd, Berndt T, Sipilä M, Paasonen P, Petäjä T, Kim S, Kurtén T, Stratmann F, Kerminen V M and Kulmala M 2012 A new atmospherically relevant oxidant of sulphur dioxide Nature 488 193
Xu K, Wang W, Wei W, Feng W, Sun Q and Li P 2017 Insights into the reaction mechanism of Criegee intermediate CH\(_{2}\)OO with methane and implications for the formation of methanol J. Phys. Chem. A 121 7236
Long B, Bao J L and Truhlar D G 2016 Atmospheric chemistry of Criegee intermediates: Unimolecular reactions and reactions with water J. Am. Chem. Soc. 138 14409
Kroll J H and Seinfeld J H 2008 Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere Atmos. Environ. 42 3593
Gutbrod R, Schindler R N, Kraka E and Cremer D 1996 Formation of oh radicals in the gas phase ozonolysis of alkenes: the unexpected role of carbonyl oxides Chem. Phys. Lett. 252 221
Herron J T and Huie R E 1978 Stopped-flow studies of the mechanisms of ozone–alkene reactions in the gas phase propene and isobutene Int. J. Chem. Kinet. 10 1019
Stone D, Blitz M, Daubney L, Howes N U M and Seakins P 2014 Kinetics of CH\(_{2}\)OO reactions with SO\(_{2}\), NO\(_{2}\), NO, H\(_{2}\)O and CH\(_{3}\)CHO as a function of pressure Phys. Chem. Chem. Phys. 16 1139
Su Y-T, Lin H-Y, Putikam R, Matsui H, Lin M C and Lee Y-P 2014 Extremely rapid self-reaction of the simplest Criegee intermediate CH\(_{2}\)OO and its implications in atmospheric chemistry Nat. Chem. 6 477
Vereecken L, Harder H and Novelli A 2012 The reaction of Criegee intermediates with NO, RO\(_{2}\), and SO\(_{2}\), and their fate in the atmosphere Phys. Chem. Chem. Phys. 14 14682
Stieb D M, Judek S and Burnett R T 2002 Meta-analysis of time-series studies of air pollution and mortality: effects of gases and particles and the influence of cause of death, age, and season J. Air Waste Manage. Assoc. 52 470
Cabezas C and Endo Y 2019 The Criegee intermediate-formic acid reaction explored by rotational spectroscopy Phys. Chem. Chem. Phys. 21 18059
Aroeira G J R, Abbott A S, Elliott S N, Turney J M and Schaefer H F 2019 The addition of methanol to Criegee intermediates Phys. Chem. Chem. Phys. 21 17760
Sun C, Xu B, Lv L and Zhang S 2019 Theoretical investigation on the reaction mechanism and kinetics of a Criegee intermediate with ethylene and acetylene Phys. Chem. Chem. Phys. 21 16583
Yin C and Takahashi K 2018 How big is the substituent dependence of the solar photolysis rate of Criegee intermediates? Phys. Chem. Chem. Phys. 20 16247
Beames J M, Liu F, Lu L and Lester M I 2013 Uv spectroscopic characterization of an alkyl substituted Criegee intermediate CH\(_{3}\)CHOO J. Chem. Phys. 138 244307
Taatjes C A, Meloni G, Selby T M, Trevitt A J, Osborn D L, Percival C J and Shallcross D E 2008 Direct observation of the gas-phase Criegee intermediate (CH\(_{2}\)OO) J. Am. Chem. Soc. 130 11883
Welz O, Savee J D, Osborn D L, Vasu S S, Percival C J, Shallcross D E and Taatjes C A 2012 Direct kinetic measurements of Criegee intermediate (CH\(_{2}\)OO) formed by reaction of CH\(_{2}\)I with O\(_{2}\) Science 335 204
Taatjes C A, Welz O, Eskola A J, Savee J D, Scheer A M, Shallcross D E, Rotavera B, Lee E P F, Dyke J M, Mok D K W, Osborn D L and Percival C J 2013 Direct measurements of conformer-dependent reactivity of the Criegee intermediate CH\(_{3}\)CHOO Science 340 177
Sršeň Š, Hollas D and Slavíček P 2018 Uv absorption of Criegee intermediates: quantitative cross sections from high-level ab initio theory Phys. Chem. Chem. Phys. 20 6421
Chhantyal-Pun R, Shannon R J, Tew D P, Caravan R L, Duchi M, Wong C, Ingham A, Feldman C, McGillen M R, Khan M A H, Antonov I O, Rotavera B, Ramasesha K, Osborn D L, Taatjes C A, Percival C J, Shallcross D E and Orr-Ewing A J 2019 Experimental and computational studies of Criegee intermediate reactions with NH\(_{3}\) and CH\(_{3}\)NH\(_{2}\). Phys. Chem. Chem. Phys. 21 14589
Li Y-L, Lin Y-H, Yin C, Takahashi K, Chiang C-Y, Chang Y-P and Lin J Jr-M 2019 Temperature-dependent rate coefficient for the reaction of CH\(_3\)SH with the simplest Criegee intermediate J. Phys. Chem. A 123 4096
Lin X, Meng Q, Feng B, Zhai Y, Li Y, Yu Y, Li Z, Shan X, Liu F, Zhang L and Sheng L 2019 Theoretical study on Criegee intermediate’s role in ozonolysis of acrylic acid J. Phys. Chem. A 123 1929
Lin Y-H, Yin C, Lin W-H, Li Y-L, Takahashi K and Lin J J 2018 Criegee intermediate reaction with alcohol is enhanced by a single water molecule J. Phys. Chem. Lett. 9 7040
Sun C, Zhang S, Yue J and Zhang S 2018 Theoretical study on the reaction mechanism and kinetics of Criegee intermediate CH\(_{2}\)OO with acrolein J. Phys. Chem. A 122 8729
Lovas F J and Suenram R D 1977 Identification of dioxirane (h2coo) in ozone-olefin reactions via microwave spectroscopy Chem. Phys. Lett. 51 453
Cabezas C, Guillemin J-C and Endo Y 2019 Fourier transform microwave spectroscopy of Criegee intermediates: The conformational behaviour of butyraldehyde oxide J. Chem. Phys. 150 104301
Chicharro D V, Poullain S M, Banares L, Hrodmarsson H R, Garcia G A and Loison J-C 2019 Threshold photoelectron spectrum of the CH\(_{2}\)OO Criegee intermediate Phys. Chem. Chem. Phys. 21 12763
Nakajima M and Endo Y 2013 Communication: Determination of the molecular structure of the simplest Criegee intermediate CH\(_{2}\)OO J. Chem. Phys. 139 101103
Lee Y-P 2015 Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates J. Chem. Phys. 143 020901
Osborn D L and Taatjes C A 2015 The physical chemistry of Criegee intermediates in the gas phase Int. Rev. Phys. Chem. 34 309
Vansco M F, Li H and Lester M I 2017 Prompt release of O 1D products upon uv excitation of CH\(_{2}\)OO Criegee intermediates J. Chem. Phys. 147 013907
Wang Z, Dyakov Y A and Bu Y 2019 Dynamics insight into isomerization and dissociation of hot Criegee intermediate CH\(_{3}\)CHOO J. Phys. Chem. A 123 1085
Watson N A, Black J A, Stonelake T M, Knowles P J and Beames J M 2018 An extended computational study of Criegee intermediate–alcohol reactions J. Phys. Chem. A 123 218
Chung C A, Su J W and Lee Y-P 2019 Detailed mechanism and kinetics of the reaction of Criegee intermediate CH\(_{2}\) OO with HCOOH investigated via infrared identification of conformers of hydroperoxymethyl formate and formic acid anhydride Phys. Chem. Chem. Phys. 21 21445
Smith C D and Karton A 2019 Kinetics and thermodynamics of reactions involving Criegee intermediates: An assessment of density functional theory and ab initio methods through comparison with ccsdt (q)/cbs data J. Comput. Chem. 9999 1
Stone D, Au K, Sime S, Medeiros D J, Blitz M, Seakins P W, Decker Z and Sheps L 2018 Unimolecular decomposition kinetics of the stabilised Criegee intermediates CH\(_{2}\)OO and CD\(_{2}\)OO Phys. Chem. Chem. Phys. 20 24940
Aplincourt P, Henon E, Bohr F and Ruiz-Lopez M F 2002 Theoretical study of photochemical processes involving singlet excited states of formaldehyde carbonyl oxide in the atmosphere Chem. Phys. 285 221
Kalinowski J, Foreman E S, Kapnas K M, Murray C, Räsänen M and Gerber R B 2016 Dynamics and spectroscopy of CH\(_{2}\)OO excited electronic states Phys. Chem. Chem. Phys. 18 10941
Trabelsi T, Kumar M and Francisco J S 2017 How does the central atom substitution impact the properties of a Criegee intermediate? Insights from multireference calculations J. Am. Chem. Soc. 139 15446
Kalinowski J, Räsänen M, Heinonen P, Kilpeläinen I and Gerber R B 2014 Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: Dynamics using a multireference potential Angew. Chem. Int. Ed. 53 265
Lee E P F, Mok D K W, Shallcross D E, Percival C J, Osborn D L, Taatjes C A and Dyke J M 2012 Spectroscopy of the simplest Criegee intermediate CH\(_{2}\)OO: Simulation of the first bands in its electronic and photoelectron spectra Chem. Eur. J. 18 12411
Meng Q and Meyer H-D 2014 A full-dimensional multilayer multiconfiguration time-dependent hartree study on the ultraviolet absorption spectrum of formaldehyde oxide J. Chem. Phys. 141 20045
Dawes R, Jiang B and Guo H 2014 Uv absorption spectrum and photodissociation channels of the simplest Criegee intermediate (CH\(_{2}\)OO) J. Am. Chem. Soc. 137 50
Samanta K, Beames J M, Lester M I and Subotnik J E 2014 Quantum dynamical investigation of the simplest Criegee intermediate CH\(_{2}\)OO and its o–o photodissociation channels J. Chem. Phys. 141 134303
Li H, Fang Y, Kidwell N M, Beames J M and Lester M I 2015 Uv photodissociation dynamics of the CH\(_{3}\)CHOO Criegee intermediate: action spectroscopy and velocity map imaging of o-atom products J. Phys. Chem. A 119 8328
Anglada J M, Bofill J M, Olivella S and Solé A 1996 Unimolecular isomerizations and oxygen atom loss in formaldehyde and acetaldehyde carbonyl oxides. A theoretical investigation J. Am. Chem. Soc. 118 4636
Cremer D, Gauss J, Kraka E, Stanton J F and Bartlett R J 1993 A ccsd (t) investigation of carbonyl oxide and dioxirane. Equilibrium geometries, dipole moments, infrared spectra, heats of formation and isomerization energies Chem. Phys. Lett. 209 547
Lehman J H, Li H, Beames J M and Lester M I 2013 Communication: Ultraviolet photodissociation dynamics of the simplest Criegee intermediate CH\(_{2}\)OO J. Chem. Phys. 139 141103
Lakshmanan S, Spada R F K, Machado F B C and Hase W L 2019 Potential energy curves for formation of the CH\(_{2}\)O\(_{2}\) Criegee intermediate on the 3CH\(_{2}\)+ 3O\(_{2}\) singlet and triplet potential energy surfaces J. Phys. Chem. A 123 8968
Li Y, Gong Q, Yue L, Wang W and Liu F 2018 Photochemistry of the simplest Criegee intermediate, CH\(_{2}\)OO: photoisomerization channel toward dioxirane revealed by caspt2 calculations and trajectory surface-hopping dynamics J. Phys. Chem. Lett. 9 978
Li H, Fang Y, Beames J M and Lester M I 2015 Velocity map imaging of o-atom products from uv photodissociation of the CH\(_{2}\)OO Criegee intermediate J. Chem. Phys. 142 214312
Li J, Carter S, Bowman J M, Dawes R, Xie D and Guo H 2014 High-level, first-principles, full-dimensional quantum calculation of the ro-vibrational spectrum of the simplest Criegee intermediate (CH\(_{2}\)OO) J. Phys. Chem. Lett. 5 2364
Yu H-G, Ndengue S, Li J, Dawes R and Guo H 2015 Vibrational energy levels of the simplest Criegee intermediate (CH\(_{2}\)OO) from full-dimensional Lanczos, mctdh, and multimode calculations J. Chem. Phys. 143 084311
Domcke W, Yarkony D and Köppel H 2004 Conical intersections: electronic structure, dynamics & spectroscopy Vol. 15 (Singapore: World Scientific)
Yarkony D R 1996 Diabolical conical intersections Rev. Mod. Phys. 68 985
Samanta K and Yarkony D R 2010 On the role of conical intersections and their local topography in the photodissociation of the 1-hydroxyethyl radical Chem. Phys. 378 110
Deskevich M P, Nesbitt D J and Werner H-J 2004 Dynamically weighted multiconfiguration self-consistent field: Multistate calculations for F+H\(_{2}\)O\(\rightarrow\) HF + OH reaction paths J. Chem. Phys. 120 7281
Wilson A K, Woon D E, Peterson K A and Dunning Jr T H 1999 Gaussian basis sets for use in correlated molecular calculations. ix. The atoms gallium through krypton J. Chem. Phys. 110 7667
Dunning Jr. T H 1989 Gaussian basis sets for use in correlated molecular calculations. i. The atoms boron through neon and hydrogen J. Chem. Phys. 90 1007
Peterson K A, Woon D E and Dunning Jr T H 1994 Benchmark calculations with correlated molecular wave functions. iv. The classical barrier height of the H+ H\(_{2}\)\(\rightarrow\) H\(_{2}\) + H reaction J. Chem. Phys. 100 7410
Sit M K, Das S and Samanta K 2023 Semiclassical dynamics on machine-learned coupled multireference potential energy surfaces: Application to the photodissociation of the simplest Criegee intermediate J. Phys. Chem. A 127 2376
Gordon M S and Schmidt M W 2005 Advances in electronic structure theory: GAMESS a decade later (Location:Elsevier)
Schmidt M W, Baldridge K K, Boatz J A, Elbert S T, Gordon M S, Jensen J H, Koseki S, Matsunaga N, Nguyen K A, Su S, Windus T L, Dupuis M and Montagomery J A 1993 General atomic and molecular electronic structure system J. Comput. Chem. 14 1347
Tully J C 1990 Molecular dynamics with electronic transitions J. Chem. Phys. 93 1061
Vetterling W T, Teukolsky S A, Press W H and Flannery B P 1989 Numerical recipes (Cambridge: Cambridge University Press)
Mai S, Marquetand P and González L 2015 A general method to describe intersystem crossing dynamics in trajectory surface hopping Int. J. Quantum Chem. 115 1215
Hammes-Schiffer S and Tully J C 1995 Nonadiabatic transition state theory and multiple potential energy surface molecular dynamics of infrequent events J. Chem. Phys. 103 8528
Bittner E R and Rossky P J 1995 Quantum decoherence in mixed quantum-classical systems: Nonadiabatic processes J. Chem. Phys. 103 8130
Schwartz B J, Bittner E R, Prezhdo O V and Rossky P J 1996 Quantum decoherence and the isotope effect in condensed phase nonadiabatic molecular dynamics simulations J. Chem. Phys. 104 5942
Wong K F and Rossky P J 2002 Solvent-induced electronic decoherence: Configuration dependent dissipative evolution for solvated electron systems J. Chem. Phys. 116 8429
Miao G and Subotnik J E 2019 Revisiting the recoherence problem in the fewest switches surface hopping algorithm J. Phys. Chem. A 123 5428
Shenvi N and Yang W 2012 Achieving partial decoherence in surface hopping through phase correction J. Chem. Phys. 137 22A528
Subotnik J E, Jain A, Landry B, Petit A, Ouyang W and Bellonzi N 2016 Understanding the surface hopping view of electronic transitions and decoherence Annu. Rev. Phys. Chem. 67 387
Shenvi N, Subotnik J E and Yang W 2011 Phase-corrected surface hopping: Correcting the phase evolution of the electronic wavefunction J. Chem. Phys. 135 024101
Subotnik J E and Shenvi N 2011 Decoherence and surface hopping: When can averaging over initial conditions help capture the effects of wave packet separation? J. Chem. Phys. 134 244114
Subotnik J E and Shenvi N 2011 A new approach to decoherence and momentum rescaling in the surface hopping algorithm J. Chem. Phys. 134 024105
Fang J-Y and Hammes-Schiffer S 1999 Improvement of the internal consistency in trajectory surface hopping J. Phys. Chem. A 103 9399
Jaeger H M, Fischer S and Prezhdo O V 2012 Decoherence-induced surface hopping J. Chem. Phys. 137 22A545
Thachuk M, Ivanov M Y and Wardlaw D M 1998 A semiclassical approach to intense-field above-threshold dissociation in the long wavelength limit. ii. Conservation principles and coherence in surface hopping J. Chem. Phys. 109 5747
Ha J-K, Lee I S and Min S K 2018 Surface hopping dynamics beyond nonadiabatic couplings for quantum coherence J. Phys. Chem. Lett. 9 1097
Fang J-Y and Hammes-Schiffer S 1997 Nonadiabatic dynamics for processes involving multiple avoided curve crossings: Double proton transfer and proton-coupled electron transfer reactions J. Chem. Phys. 107 8933
Granucci G and Persico M 2007 Critical appraisal of the fewest switches algorithm for surface hopping J. Chem. Phys. 126 134114
Esposito V J, Liu T, Wang G, Caracciolo A, Vansco M F, Marchetti B, Karsili T N V and Lester M I 2021 Photodissociation dynamics of CH\(_{2}\)OO on multiple potential energy surfaces: Experiment and theory J. Phys. Chem. A 125 6571
Antwi E, Bush R E, Marchetti B and Karsili T N V 2022 A direct dynamics study of the exotic photochemistry of the simplest Criegee intermediate, CH\(_{2}\)OO Phys. Chem. Chem. Phys. 24 16724
Acknowledgements
The authors would like to thank Indian Institute of Technology Bhubaneswar for infrastructural support. In addition, KS would like to acknowledge the support from DST-SERB through a research grant CRG/2020/001895.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sit, M.K., Das, S., Kumar, P. et al. Photodissociation pathways in the simplest Criegee intermediate: a semi-classical investigation. J Chem Sci 135, 82 (2023). https://doi.org/10.1007/s12039-023-02197-8
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1007/s12039-023-02197-8