Potential energy surfaces of carbon dioxide

Xantheas, Sotiris S.; Ruedenberg, Klaus

doi:10.1002/qua.560490408

Cited by 25 publications

(25 citation statements)

References 32 publications

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“…The transition state of the ground state is very close to the local bend minimum. The present calculation is basically in agreement with the result obtained by Xantheas and Ruedenberg, 29 which estimate the saddle point at R co = 1.32 Å and α = 94.2 • with a potential barrier of 0.607 eV above the local bend minimum. All other four excited states 1 A 2 , 3 A 2 , 1 B 2 , and 3 B 2 are quite similar to the ground state 1 A 1 , and they all have double-well structures.…”

Section: D Potential Energy Surfaces For Bent Valence Excited Stasupporting

confidence: 92%

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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Section: D Potential Energy Surfaces For Bent Valence Excited Stasupporting

confidence: 92%

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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“…1a is two dimensional contour plots of the CASPT2 PES for the 1 A 1 state of CO 2 . It can be seen that there are two local minimum on the 1 A 1 state PES of CO 2 , which is supported by Xantheas and Ruedenberg's work [26]. For 1 B 2 and 3 B 2 state, there is only one local minimum within the range of 1.8 bohr < R CO < 4.0 bohr and 70° < α OCO < 180° and this minimum around α OCO = 120° (see Figs.…”

Section: The Potential Energy Surfaces Of 1 a 1 ( ) 1 B 2 And 3 B supporting

confidence: 62%

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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“…This minimum is located 6.03 eV above the global one, again in good agreement with the previous findings. 23,24 The fundamental excitations in the OCO well, calculated for N CO2 = 0, are ω a = 680 cm −1 , ω b = 720 cm −1 , and ω s = 1550 cm −1 . For the linear COO, the calculated CO and OO bond lengths are identical to the ones given in Ref.…”

Section: Electronic Structure Calculationsmentioning

confidence: 99%

Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces

Grebenshchikov

2013

The Journal of Chemical Physics

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The global potential energy surfaces of the first six singlet electronic states of CO2, 1-3(1)A', and 1-3(1)A" are constructed using high level ab initio calculations. In linear molecule, they correspond to X̃(1)Σg (+), 1(1)Δu, 1(1)Σu (-), and 1(1)Πg. The calculations accurately reproduce the known benchmarks for all states and establish missing benchmarks for future calculations. The calculated states strongly interact at avoided crossings and true intersections, both conical and glancing. Near degeneracies can be found for each pair of six states and many intersections involve more than two states. In particular, a fivefold intersection dominates the Franck-Condon zone for the ultraviolet excitation from the ground electronic state. The seam of this intersection traces out a closed loop. All states are diabatized, and a diabatic 5 × 5 potential matrix is constructed, which can be used in quantum mechanical calculations of the absorption spectrum of the five excited singlet valence states.

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Potential energy surfaces of carbon dioxide

Cited by 25 publications

References 32 publications

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

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

Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces

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