Collisional Excitation of CO Molecules by O(1D) Atoms

Abe, Makoto; Inagaki, Yoshio; Springsteen, L. L.; Matsumi, Yutaka; Kawasaki, Masahiro; Tachikawa, Hiroto

doi:10.1021/j100099a030

Cited by 20 publications

(40 citation statements)

References 4 publications

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“…In the photolysis of phenol at 193 nm, the available energy of 148 kcal mol −1 above C 6 H 5 OH is near that of the reaction O͑ 1 D͒ +C 6 H 6 , 149+ 10= 159 kcal mol −1 ; the kinetic energy of O͑ 1 D͒, produced upon photolysis of O 3 at 248 nm, with respect to the CM for O͑ 1 D͒ +C 6 H 6 was reported to be 10.2 kcal mol −1 . 90 Previous experiments on photolysis of phenol at 193 nm indicated a nascent rotational temperature of ϳ4600 K for CO ͑ =1-4͒ and an observed vibrational distribution of ͑ =1͒ : ͑ =2͒ : ͑ =3͒ : ͑ =4͒ = 64.3: 22.2: 9.1: 4.4 corresponding to a vibrational temperature of 3350Ϯ 20 K; an average rotational energy of 6.9Ϯ 0.7 kcal mol 1 and vibrational energy of 3.8Ϯ 0.7 kcal mol −1 were derived. 44 In the present work on O͑ 1 D͒ +C 6 H 6 , the CO product shows less rotational excitation ͑2.4Ϯ 0.4 kcal mol −1 ͒ but greater vibrational excitation ͑8.0Ϯ 0.7 kcal mol −1 ͒.…”

Section: B Channels To Produce Comentioning

confidence: 99%

Dynamics of reactions O(D1)+C6H6 and C6D6

Chen

Liang

Lin

et al. 2008

The Journal of Chemical Physics

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The reaction between O((1)D) and C(6)H(6) (or C(6)D(6)) was investigated with crossed-molecular-beam reactive scattering and time-resolved Fourier-transform infrared spectroscopy. From the crossed-molecular-beam experiments, four product channels were identified. The major channel is the formation of three fragments CO+C(5)H(5)+H; the channels for formation of C(5)H(6)+CO and C(6)H(5)O+H from O((1)D)+C(6)H(6) and OD+C(6)D(5) from O((1)D)+C(6)D(6) are minor. The angular distributions for the formation of CO and H indicate a mechanism involving a long-lived collision complex. Rotationally resolved infrared emission spectra of CO (12.9 for O((1)D)+C(6)D(6) is consistent with the expectation for an abstraction reaction. The mechanism of the reaction may be understood from considering the energetics of the intermediate species and transition states calculated at the G2M(CC5) level of theory for the O((1)D)+C(6)H(6) reaction. The experimentally observed branching ratios and deuterium isotope effect are consistent with those predicted from calculations.

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Section: B Channels To Produce Comentioning

confidence: 99%

Dynamics of reactions O(D1)+C6H6 and C6D6

Chen

Liang

Lin

et al. 2008

The Journal of Chemical Physics

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“…The collisions of O( 3 P, 1 D) with CO( 1 + ) have been widely studied both experimentally and theoretically. [1][2][3][4][5][6] A large amount of electronic energy can be efficiently transferred through a spin-orbit induced surface/conical intersection involving a long-lived (several vibrations) collision complex intermediates. The vibrational relaxation of CO( 1 + ) by O( 3 P) is several orders of magnitude faster than predicted by the conventional theory of translational to vibrational energy transfer.…”

Section: Introductionmentioning

confidence: 99%

“…However, by using the complete active space self consistent field (CASSCF) and multireference configuration interaction (MRCI) methods, Spielfiedel et al 12 found that there are surface crossing regions between 1 B 2 and 3 B 2 states at CO bond length R CO = 1.243 Å and OCO bond angle in 90 • < α OCO <100 • . Spielfiedel et al 12 also pointed out that the predissociation of 1 B 2 state can occur through a triplet state 3 A 2 intersection with the singlet state 1 B 2 . Therefore, it is still not very clear whether or not the 1 B 2 state has intersection with 3 A 2 state or/and 3 B 2 state.…”

Section: Introductionmentioning

confidence: 99%

Topology of conical/surface intersections among five low-lying electronic states of CO2: Multireference configuration interaction calculations

Zhou

Zhu

Wen

et al. 2013

The Journal of Chemical Physics

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Multi-reference configuration interaction with single and double excitation method has been utilized to calculate the potential energy surfaces of the five low-lying electronic states (1)A1, (1)A2, (3)A2, (1)B2, and (3)B2 of carbon dioxide molecule. Topology of intersections among these five states has been fully analyzed and is associated with double-well potential energy structure for every electronic state. The analytical potential energy surfaces based on the reproducing kernel Hilbert space method have been utilized for illustrating topology of surface crossings. Double surface seam lines between (1)A1 and (3)B2 states have been found inside which the (3)B2 state is always lower in potential energy than the (1)A1 state, and thus it leads to an angle bias collision dynamics. Several conical∕surface intersections among these five low-lying states have been found to enrich dissociation pathways, and predissociation can even prefer bent-geometry channels. Especially, the dissociation of O((3)P) + CO can take place through the intersection between (3)B2 and (1)B2 states, and the intersection between (3)A2 and (1)B2 states.

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“…Their calculations indicated that no crossing point was found between 1 B 2 and 3 B 2 state. However, in Abe et al work [11], they pointed that the seam between the 1 B 2 and 3 B 2 state surfaces ranges from α OCO = 100° to 130°, R CO = 1.2-1.5 Å for the bond length of the new CO bond; and in Spielfiedel et al paper [18], there is a crossing point between 1 B 2 and 3 B 2 state when R CO = 2.35 bohr and 90° < α OCO < 100°.…”

Section: Introductionmentioning

confidence: 93%

“…For example, CO 2 photodissociation at 157 nm which involves state to state correlations between CO (ν) and O ( 3 P) has been studied up to now [1][2][3][4][5][6]. Moreover, the reaction of CO (ν) with the elec tronic ground state oxygen atom O ( 3 P) has also been studied with experimental [7][8][9][10][11][12][13][14] and theoretical methods [15,16] so far. However, a full understanding of these two questions is hampered by the complex nature of its electronically excited states.…”

Section: Introductionmentioning

confidence: 99%

The potential energy surfaces of the ground and excited states of carbon dioxide molecule

Peng

Zhang

et al. 2014

Russ. J. Phys. Chem.

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Potential energy surfaces (PESs) of the 1 A l ( ), 1 B 2 and 3 B 2 electronic states of CO 2 have been computed as a function of the two bond distances and the bond angle. The calculations were based on the complete active space self consistent field (CASSCF) and multiconfigurational second order perturbation theory (CASPT2) electronic structure models. From our calculations no crossing point between 1 B 2 and 3 B 2 states was found, but there is a crossing point located between 1 B 2 and 3 A 2 state on the PESs. The energy of the crossing point is lie 0.23 eV above the CO + O ( 3 P), which is in agreement with the value of 0.27 eV on the experiment. This implies that the mechanism of the recombination of an oxygen atom with a carbon monoxide molecule: CO(X 1 Σ + , ν) + O( 3 P) 3 C 1 C CO(X 1 Σ + , ν = 0) + O( 1 D) may occur through the 3 A 2 state crossing the 1 B 2 state. The equilibrium geometries and adiabatic excitation energies of 1,3 B 2 , 1,3 A 2 states of CO 2 were reported and discussed in this paper, too.

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Collisional Excitation of CO Molecules by O(1D) Atoms

Cited by 20 publications

References 4 publications

Dynamics of reactions O(D1)+C6H6 and C6D6

Dynamics of reactions O(D1)+C6H6 and C6D6

Topology of conical/surface intersections among five low-lying electronic states of CO2: Multireference configuration interaction calculations

The potential energy surfaces of the ground and excited states of carbon dioxide molecule

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