Photochemistry of the Simplest Criegee Intermediate, CH2OO

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Photochemistry of the Simplest Criegee Intermediate, CHOO: Photoisomerization Channel Towards Dioxirane Revealed by CASPT2 Calculations and Trajectory Surface-Hopping Dynamics Yazhen Li, Qianqian Gong, Ling Yue, Wenliang Wang, and Fengyi Liu J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.8b00023 • Publication Date (Web): 08 Feb 2018 Downloaded from http://pubs.acs.org on February 10, 2018

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The Journal of Physical Chemistry Letters

Photochemistry of the Simplest Criegee Intermediate, CH2OO: Photoisomerization Channel towards Dioxirane Revealed by CASPT2 Calculations and Trajectory Surface-Hopping Dynamics Yazhen Li1, Qianqian Gong1, Ling Yue2, Wenliang Wang1,* and Fengyi Liu1,* 1. Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710062, P. R. China 2. School of Sciences, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, P. R. China Corresponding Author * Fengyi Liu: [email protected] * Wenliang Wang: [email protected]

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ABSTRACT: Photochemistry of Criegee intermediates play a significant role in atmospheric chemistry, but it is relatively less explored compared with their thermal reactions. Using the multireference CASPT2 electronic structure calculations and CASSCF trajectory surfacehopping

molecular

dynamics,

we

have

revealed

a

dark-state-involved

A1A→X1A

photoisomerization channel of the simple Criegee intermediate (CH2OO) that leads to a cyclic dioxirane. The excited molecules on A1A state, which can be either originated from B1A state via B1A→A1A internal conversion or formed by state-selectively electronic excitation, is driven by the out-of-plane motion towards a perpendicular A/X1A minimal-energy crossing point (MECI), then radiationlessly decay to the ground state with an average time constant of ~138 fs, finally form dioxirane at ~ 254 fs. The dynamics starting from the A1A state show that the quantum yield of photoisomerization from the simple Criegee intermediate to dioxirane is 38%. The finding of A1A→X1A photoisomerization channel is expected to broaden the reactivity profile and deepen the understanding in photochemistry of Criegee intermediates.

TOC GRAPHICS

KEYWORDS: Criegee Intermediates, Trajectory Surface-Hopping Molecular Dynamics, Dioxirane, Photoisomerization, Nonadiabatic Transition


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Criegee intermediate (CI), first proposed by Criegee in 1949 as the ozonolysis product of ethylene[1], has been recently recognized as an important reactive intermediate in atmospheric chemistry[2-4]. Criegee intermediates can participate in many bimolecular reactions, such as reacting with the atmospherically-abundant H2O, NO, NO2 and SO2 molecules, etc[5-14], as well as self-reacting[15,16] to generate various metastable species (OH, HCHO, 1O2, etc). The reactions can either take place in gas-phase or at the air/water interface[17,18], without or with catalysts[19,20]. In addition to bimolecular reactions, the unimolecular processes of Criegee intermediates including bond dissociations and isomerizations have also drawn great attentions of both experimentalists[21-27] and theoreticians[27-32]. Recently, IR spectroscopic[21] and theoretical calculations[31-35] have revealed a thermal isomerization channel towards an energetically more favorable dioxirane, which can act as an oxidant to involve in further reactions. Since Criegee intermediate is mostly abundant in troposphere where sunlight is plenty in the daytime, its photophysics and photochemistry are expected to important (although experiments show that the photochemical reactions of CI with reported loss rates of a few s-1 [22] do not contribute that much compared with the thermal consumptions, including unimolecular and water reactions). The UV absorption spectra (B1A′ ← X1A′) of simplest and substituted Criegee intermediates have been reported by Li, Beames, Ting and Sheps, et al[4,36-38]; in the meantime, the photo-induced reactions (e.g., the O-O or C-O bond cleavages) have also been the focus of several recent experimental and high-level theoretical studied[23,28,30,38,39]. On the basis of multireference ab initio calculations, Guo et al revealed that the excited molecules on B1A′ electronic states (under a Cs symmetry) tend to rupture the O-O bond and dissociate via two spinallowed channels, that is, H2CO X1A1 + O 1D and H2CO a3A′′ + O 3P[39]; the latter was also confirmed as the dominant channel by molecular dynamic simulations by Lester and


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coworkers[28]. These milestone investigations provided fundamental insights and lay solid foundations for further extensive photochemical studies of Criegee intermediates. In this communication, we reported the multireference ab initio quantum chemistry calculations on the photo-induced unimolecular reactions of the simplest Criegee intermediate (simplest CI, i.e., CH2OO) by mean of comprehensive CASPT2[40] potential energy surface (PESs) explorations and on-the-fly CASSCF[41] trajectory surface-hopping (TSH) [42,43] molecular dynamics. Besides confirming the known O-O photocleavage mechanism, we have for the first time located a possible S1(A1A) excited-state nonadiabatic photoisomerization channel leading to a ground-state cyclic dioxirane. The finding of A1A→X1A photoisomerization channel not only deepens the knowledge on photochemistry of Criegee intermediates, but also suggests new opportunities for effective control of their photochemical reactions. The SA8-CASSCF(14e,10o)/ANO-RCC-VTZP[44,45] calculated potential energy curves (PECs) for the lowest three singlet states are shown in Figure 1 (For clarity, PECs of other states are omitted; a full energy profile is provided in supporting information, Figure S1; and the active orbitals are shown in Figure S2). The optimized S0 minimum, with C-O and O-O distances of 1.289 and 1.331 Å, respectively, demonstrates a zwitterion nature of the Criegee intermediates, which is consistent with previous experimental demonstration[46]. The PECs are obtained by a relaxed scanning of O-O distance without symmetry constraints applied. The X1A, A1A and B1A states under C1 symmetry respectively correspond to the X1A′, A1A′′ and B1A′ state in previous studies with a Cs symmetric constraint[28,39]. The CASSCF-PESs here qualitatively reproduce the Dynamically-Weighted (DW)-SA-CASSCF(12e,11o) computed ones, that is, both the A1A and B1A states are attractive states in short O-O distance region (< 2.0 Å) and thus have excited-state minima. In addition, the potential energy well for B1A minimum is much shallower than A1A,


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thus the CASSCF PECs suggest that the photo excitation from X1A to B1A readily leads to the unimolecular dissociation via O-O bond cleavage.

Figure 1. The CASSCF(14e,10o)/ANO-RCC-VTZP computed O-O dissociation energy profiles for ground state X1A and the lowest two excited singlet states, A1A and B1A. Energies are relative to the ground-state energy of X-CH2OO. The S0, S1 and S2 minimums are respectively presented in hollow cycles. Although the in-plane PECs may account for the photodissociation of simplest CI, they are incapable of describing photo-induced processes involving out-of-plane degree of freedoms. In both the A1A and B1A states, the elongated O-O bond has a considerable tendency to rotate out of the molecular plane. Therefore, we carried out two-dimensional (2-D) scanning at the MSCASPT2(14e,10o)/ANO-RCC-VTZP level, choosing the H-C-O1-O2 dihedral angle (φ) and CO2 distance as independent variables. The C-O2 distance is considered as an effective indicator to balancedly describe the O-O cleavage and isomerization channel (e.g., towards dioxirane).


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The computed 2-D PESs, along with the optimized geometries of key structures, are summarized in Figure 2.

Figure 2. The MS-CASPT2(14e,10o)/ANO-RCC-VDZP optimized geometries of key structures including minima (min), transition state (TS) and minimal-energy crossing points (MECIs)[47,48] (top panel); and the CASSCF(14e,10o)/ANO-RCC-VDZP computed 2D PESs with respected to the C-O2 distance and H-C-O1-O2 dihedral angle (φ) of CH2OO (bottom panel). The relatively extensive CASSCF-PESs (which is


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qualitatively consistent with CASPT2-PESs) are presented for illustration purpose and the CASPT2-PESs are provided in Supporting Information, Figure S5 and S6. As seen in Figure 2, the minimal-energy paths (MEPs) on X- and B-state PESs (shown as black and green dash curves at the front edges) are consistent with those obtained by in-plane OO cleavage PECs (Figure 1). It implies that once the molecules are excited to the bright B1A state, they are most likely to undergo dissociative channel following an in-plane pattern. In the meantime, the PES of the dark S1 state shows an alternative landscape: The S1-MEP no longer coincides with the in-plane O-O cleavage PEC (red dash curve), due to the existence of a broad and deep funnel found around C-O2 distance of ~2.1 Å (corresponding O-O distance of 1.381 Å) and φ of 96.9°. As shown in Figure 2 (and in Figure S4 and S6, top panels), at the bottom of the potential energy well, a MECI between X and A1A states (X/A-CI, Figure 2) was optimized at the MS-CASPT2(14e,10o) level, whose projection on X1A -PES falls on the left rear of the ridge between the simplest CI and dioxirane isomers. Those findings in total suggest that if the excited CH2OO molecules have chance to populate to A1A state, they will be driven by the out-of-plane motion and easily decay towards a deep funnel, then undergo nonadiabatic transition to reach ground state, leading to either the simplest CI or more likely an energetically-favorable isomer, dioxirane. The photoisomerization channel, in addition to the thermal transformation, will together contribute to the formation of dioxirane in atmosphere. Of course, since the nonadiabatic coupling between B1A and A1A states is inefficient at the planar geometries of simplest CI, the photoisomerization channel found here is less likely to be the dominant one among the overall photo-induced processes. The unveiled photoisomerization channel provides important implications for the photochemistry of substituted Criegee intermediates with considerable off-plane distortions, as well as for state-selective spectroscopic studies.


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To demonstrate the A1A→X1A photoisomerization mechanism, we carried out trajectory surface-hopping dynamics at the CASSCF(14e,10o)/def-SVP[49] level. The trajectories are initially populated to A1A state (to avoid of the low efficient internal conversion from B to A1A state). The choosing of CASSCF method majorly considers the computational costs, and the validity of CASSCF has been proved by the good consistency with MS-CASPT2 PES, especially for the X1A and A1A states (Seen in Figure S3 and S5, respectively). More details of TSH setup are provided in supporting information. A representive trajectory leading to the ground-state dioxirane is shown in Figure 3, and those for Z/E isomerization and O-O bond cleavage are shown in supporting information (Figure S7 and S8).

Figure 3. A representive trajectory in TSH molecular dynamics. (a) The variation of CASSCF energies of three investigated states; the tracking state (force state) are emphasized in purple; (b) and (c) the geometry variations of CH2OO during the simulation. The


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black vertical line indicates the snapshot when the bond length of C-O2 first reaches 1.5 Å (equals to C-O1 distance) and thus dioxirane ring begins to form.

Under the given initial conditions, 72% percent of the total 74 successful trajectories undergo the photoisomerization channel (including both the ring-closure and Z/E isomerizations) and the remainder follows an O-O bond cleavage mechanism. The trajectories corresponding to photoisomerization channels have an average A1A lifetime of 138 fs before hopping into the ground state; then after 116 fs, the three-membered-ring dioxirane structures are finally formed. When starting from the A1A state, the quantum yields for ring-closure isomerization are 38%. In conclusion, a new A1A→X1A photoisomerization channel of simple Criegee intermediate towards dioxirane was revealed by MS-CASPT2 electronic structure calculations and CASSCF TSH molecular dynamics. The excited molecules on A1A state, which are either originated from B1A state via internal conversion or state-selectively electronic excitation, will be driven by the out-of-plane motion towards a perpendicular A/X1A MECI with a time constant of ~140 fs, then radiationlessly decay to ground state and form the dioxirane in ~116 fs with a quantum yields of 38% (When starting from the A1A state). The finding of A1A→X1A photoisomerization channel is expected to broaden the reactivity profile and deepen the understanding in photochemistry of Criegee intermediates.

Supporting Information. The following files are available free of charge. The CASSCF and CASPT2 computed PESs, the Cartesian coordinates of important geometries (pdf), as well as the ensemble and representive trajectories of TSH dynamics (pdf & movie).


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Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work is supported by grants from the NSFC (Grant Nos. 21473107, 21473108, 21636006) and Fundamental Research Funds for the Central Universities (Grant No. GK201502002).

REFERENCES (1) Criegee, R.; Wenner, G. Die Ozonisierung des 9,10-Oktalins. Eur. J. Org. Chem. 1949, 564, 9-15. (2) Johnson, D.; Marston, G. The Gas-phase Ozonolysis of Unsaturated Volatile Organic Compounds in the Troposphere. Chem. Soc. Rev. 2008, 37, 699-716. (3) Criegee, R. Mechanism of Ozonolysis. Angew. Chem. Int. Ed. 1975, 14, 745-752. (4) Lee, Y. P. Perspective: Spectroscopy and Kinetics of Small Gaseous Criegee Intermediates. J. Chem. Phys. 2015, 143, 020901. (5) Vereecken, L.; Francisco, J. S. Theoretical Studies of Atmospheric Reaction Mechanisms in the Troposphere. Chem. Soc. Rev.2012, 41, 6259-6293. (6) Long, B.; Bao, J.L.; Truhlar, D.G. Atmospheric Chemistry of Criegee Intermediates: Unimolecular Reactions and Reactions with Water. J. Am. Chem. Soc. 2016, 138, 14409-14422.


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Page 11 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(7) Smith, M. C.; Chang, C.-H.; Chao, W.; Lin, L.-C.; Takahashi, K.; Boering, K. A.; Lin, J. J.-M. Strong Negative Temperature Dependence of the Simplest Criegee Intermediate CH2OO Reaction with Water Dimer. J. Phys. Chem. Lett.2015, 6, 2708–2713. (8) Foreman, E. S.; Kapnas, K. M.; Murray, C. Reactions between Criegee Intermediates and the Inorganic Acids HCland HNO3: Kinetics and Atmospheric Implications. Angew. Chem. Int. Ed. 2016, 55, 10419–10422. (9) Vereecken, L. The Reaction of Criegee Intermediates with Acids and Enols. Phys. Chem. Chem. Phys. 2017, 19, 28630–28640. (10) Vereecken, L.; Harder, H.; Novelli, A. The Reaction of Criegee Intermediates with NO, RO2, and SO2, and Their Fate in the Atmosphere. Phys. Chem. Chem. Phys.2012,14, 14682-14695. (11) Hasson, A. S.; Chung, M. Y.; Kuwata, K. T.; Converse, A. D.; Krohn, D.; Paulson, S. E. Reaction of Criegee Intermediates with Water Vapors—An Additional Source of OH Radicals in Alkene Ozonolysis? J. Phys. Chem. A. 2003, 107, 6176-6182. (12) Stone, D.; Blitz, M.; Daubney, L.; Howes, N.U.; Seakins, P. Kinetics of CH2OO Reactions with SO2, NO2, NO,H2O and CH3CHO as A Function of Pressure. Phys. Chem. Chem. Phys. 2014, 16, 1139-1149. (13) Taatjes, C.A.; Shallcross, D.E.; Percival, C.J. Research Frontiers in the Chemistry of Criegee Intermediates and Tropospheric Ozonolysis. Phys. Chem. Chem. Phys. 2014, 16, 1704-1718.


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Page 12 of 16

(14) Xu, K.; Wang, W.; Wei, W.; Feng, W.; Sun, Q.; Li, P. Insights into the Reaction Mechanism of Criegee IntermediateCH2OO with Methane and Implications for the Formation of Methanol. J. Phys. Chem. A. 2017, 121, 7236-7245. (15) Su, Y.T.; Lin, H.Y.; Putikam, R.; Matsui, H.; Lin, M.C.; Lee, Y.P. Extremely Rapid Self-reaction of the Simplest Criegee Intermediate CH2OO and Its Implications in Atmospheric Chemistry. Nat. Chem. 2014, 6, 477–483. (16) Chhantyal-Pun, R.; Davey, A.; Shallcross, D. E.; Percival, C. J.; Orr-Ewing, A. J.A Kinetic Study of the CH2OO Criegee Intermediate Self-reaction, Reaction with SO2 and Unimolecular Reaction Using Cavity Ring-down Spectroscopy. Phys. Chem. Chem. Phys. 2015, 17, 3617–3626. (17) Zhong, J.; Kumar, M.; Zhu, C. Q.; Francisco, J. S.; Zeng, X. C. Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces. Angew. Chem. Int. Ed. 2017, 56, 7740–7744. (18) Kumar, M.; Zhong, J.; Francisco, J. S.; Zeng, X. C. Criegee Intermediate-hydrogen Sulfide Chemistry at the Air/Water Interface. Chem. Sci. 2017, 8, 5385–5391. (19) Raghunath, P.; Lee, Y. P.; Lin, M. C. Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO. J. Phys. Chem. A. 2017, 121, 3871–3878. (20) Kumar, M.; Busch, D. H.; Subramaniam, B.; Thompson, W. H. Barrierless Tautomerization of Criegee Intermediates via Acid Catalysis. Phys. Chem. Chem. Phys. 2014, 16, 22968–22973.


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(21) Su, Y.T.; Huang, Y.H.; Witek, H.A.; Lee, Y.P. Infrared Absorption Spectrum of the Simplest Criegee Intermediate CH2OO. Science 2013, 340, 174-176. (22) Beames J.M.; Liu, F.; Lu, L.; Lester, M.I. Ultraviolet Spectrum and Photochemistry of the Simplest Criegee Intermediate CH2OO. J. Am. Chem. Soc. 2012, 134, 20045-20048. (23) Li, H.; Fang, Y.; Beames, J.M.; Lester, M.I. Velocity Map Imaging of O-atom Products from UV Photodissociation of the CH2OO Criegee Intermediate. J. Chem. Phys. 2015, 142, 214312-214317. (24) Wiens, J.P.; Shuman, N.S.; Viggiano, A.A. Production of and Dissociative Electron Attachment to the Simplest Criegee Intermediate in An Afterglow. J. Phys. Chem. Lett. 2015, 6, 383-387. (25) Lehman, J. H.; Li, H.; Beames, J. M.; Lester, M. I. Communication: Ultraviolet Photodissociation Dynamics of the Simplest Criegee Intermediate CH2OO. J. Chem. Phys. 2013, 139, 699. (26) Fang, Y.; Liu, F.; Barber, V.P.; Klippenstein, S.J.; Mccoy, A.B; Lester, M.I. Deep Tunneling in the Unimolecular Decay of CH3CHOO Criegee Intermediates to OH Radical Products. J. Chem. Phys. 2016, 145, 234308. (27) Trabelsi, T.; Kumar, M.; Francisco, J. S. How Does the Central Atom Substitution Impact the Properties of Criegee Intermediate? Insights from Multi-Reference Calculations. J. Am. Chem. Soc. 2017, 139, 15446-15449.


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(28) Samanta, K.; Beames, J.M.; Lester, M.I.; Subotnik, J.E. Quantum Dynamical Investigation of the Simplest Criegee Intermediate CH2OO and Its O–O Photodissociation Channels. J. Chem. Phys. 2014,141, 745. (29) Aplincourt, P.; Henon, E.; Bohr, F.; Ruiz-López, M.F. Theoretical Study of Photochemical Processes Involving Singlet Excited States of Formaldehyde Carbonyl Oxide in the Atmosphere. Chem. Phys. 2002,285, 221-231. (30) Kalinowski, J.; Foreman, E.S.; Kapnas, K.M.; Murray, C.; Räsänen, M.; Gerber, R.B. Dynamics and Spectroscopy of CH2OO Excited Electronic States. Phys. Chem. Chem. Phys. 2016, 18, 10941-10946. (31) Kalinowski, J.; Räsänen, M.; Heinonen, P.; Kilpeläinen, I.; Gerber, R.B. Isomerization and Decomposition of a Criegee Intermediate in the Ozonolysis of Alkenes: Dynamics Using a Multireference Potential. Angew. Chem. Int. Ed. 2014, 53, 265. (32) Nguyen, T.N.; Putikam, R.; Lin, M.C.A Novel and Facile Decay Path of Criegee Intermediates by Intramolecular Insertion Reactions via Roaming Transition States. J. Chem. Phys. 2015, 143, 167101. (33) Yin, C.; Takahashi, K. How does Substitution Affect the Unimolecular Reaction Rates of Criegee Intermediates? Phys. Chem. Chem. Phys. 2017, 19, 12075-12084. (34) Li, J.; Carter, S.; Bowman, J.M.; Dawes, R.; Xie, D.; Guo, H. High-Level, FirstPrinciples, Full-Dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH2OO). J. Phys. Chem. Lett. 2014, 5, 2364.


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Page 15 of 16 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(35) Kalinowski, J.; Heinonen, P.; Kilpeläinen, I.A.; Rasanen, M.; Gerber, R.B. Stability of Criegee Intermediates Formed by Ozonolysis of Different Double Bonds. J. Phys. Chem. A. 2015, 119, 2318-2325. (36) Ting, W.-L.; Chen, Y.-H.; Chao, W.; Smith, M. C.; Lin, J. J.-M. The UV Absorption Spectrum of the Simplest Criegee Intermediate CH2OO. Phys. Chem. Chem. Phys. 2014, 16, 10438–10443. (37) Sheps, L.; Scully, A. M.; Au, K. UV Absorption Probing of the Conformer-dependent Reactivity of a Criegee Intermediate CH3CHOO. Phys. Chem. Chem. Phys. 2014, 16, 26701–26706. (38) Beames, J.M.; Liu, F.; Lu, L.; Lester, M.I. UV Spectroscopic Characterization of An Alkyl Substituted Criegee Intermediate CH3CHOO. J. Chem. Phys. 2013, 138, 745. (39) Dawes, R.; Jiang, B.; Guo, H. UV Absorption Spectrum and Photodissociation Channels of the Simplest Criegee Intermediate (CH2OO). J. Am. Chem. Soc. 2015, 137, 50-53. (40) Finley, J.; Malmqvist, P.Å.; Roos, B.O.; Serrano-Andrés, L. The Multi-state CASPT2 Method. Chem. Phys. Lett. 1998, 288, 299-306. (41) Malmqvist, P.Å.; Roos, B.O.; Schimmelpfennig, B. The Restricted Active Space (RAS) State Interaction Approach with Spin-orbit Coupling. Chem. Phys. Lett. 2002, 357, 230240. (42) Barbatti, M. Nonadiabatic Dynamics with Trajectory Surface Hopping Method. WIREs. Comp. Mol. Sci. 2011, 1, 620-633.


15


Page 16 of 16

(43) Mai, S.; Richter, M.; Ruckenbauer, M.; Oppel, M.; Marquetand, P.; González, L. SHARC: Surface Hopping Including Arbitrary Couplings-Program Package for NonAdiabatic Dynamics. sharc-md.org, 2014. (44) Roos, B.O.; Lindh, R.; Malmqvist, P.Å.; Veryazov, V.; Widmark, P.O. Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set. J. Phys. Chem. A. 2004, 108, 2851-2858. (45) Roos, B.O.; Lindh, R.; Malmqvist, P. Å.; Veryazov, V.; Widmark, P.O. New Relativistic ANO Basis Sets for Transition Metal Atoms. J. Phys. Chem. A. 2005, 109, 6575-6579. (46) Nakajima, M.; Endo, Y. Communication: Determination of the Molecular Structure of the Simplest Criegee Intermediate CH2OO. J. Chem. Phys. 2013, 139, 101103. (47) Levine, B.G. Martínez, T.J. Isomerization through Conical Intersections. Annu. Rev. Phys. Chem. 2007, 58, 613-634. (48) Yarkony, D.R. Conical Intersections: Diabolical and Often Misunderstood. Acc. Chem. Res. 1998, 31, 511-518. (49) Schäfer, A. Fully Optimized Contracted Gaussian Basis Sets for Atoms Li to Kr. J. Chem. Phys. 1992, 97, 2571-2577.


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Photochemistry of the Simplest Criegee Intermediate, CH2OO

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