Photodissociation of ozone in the Hartley band: Potential energy surfaces, nonadiabatic couplings, and singlet/triplet branching ratio

Schinke, Reinhard; McBane, George C.

doi:10.1063/1.3299249

Cited by 60 publications

(93 citation statements)

References 67 publications

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“…The O 3 absorption spectrum in the region 200-1100 nm consists of four absorption bands (Hartley, Huggins, Chappuis, and Wulf). Quantum mechanical dynamics calculations on potential energy surfaces explain the principal features of the O 3 spectrum in the UV, visible and near infrafed (NIR) wavelength regions (Banichevich et al, 1993;Grebenshchikov et al, 2007;Schinke and McBane, 2010). The assignment of absorption bands from nine electronic states was very comprehensibly illustrated using one-dimensional cuts through the potential energy surfaces (Grebenshchikov et al, 2007).…”

Section: Introductionmentioning

confidence: 99%

High spectral resolution ozone absorption cross-sections – Part 1: Measurements, data analysis and comparison with previous measurements around 293 K

et al. 2014

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Abstract. In this paper we discuss the methodology of taking broadband relative and absolute measurements of ozone cross-sections including uncertainty budget, experimental set-ups, and methods for data analysis. We report on new ozone absorption cross-section measurements in the solar spectral region using a combination of Fourier transform and echelle spectrometers. The new cross-sections cover the spectral range 213-1100 nm at a spectral resolution of 0.02-0.06 nm in the UV-visible and 0.12-0.24 nm in the IR at eleven temperatures from 193 to 293 K in steps of 10 K. The absolute accuracy is better than three percent for most parts of the spectral region and wavelength calibration accuracy is better than 0.005 nm.The new room temperature cross-section data are compared in detail with previously available literature data. The temperature dependence of our cross-sections is described in a companion paper (Serdyuchenko et al., 2014).

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Section: Introductionmentioning

confidence: 99%

High spectral resolution ozone absorption cross-sections – Part 1: Measurements, data analysis and comparison with previous measurements around 293 K

et al. 2014

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“…Classical calculations were performed both without the nonadiabatic coupling to the X state and including it by means of the trajectory surface hopping (TSH) method. 34,35 In the TSH method the coupling between states A and X was taken asγ D γ , where D γ is the NACME defined in Eq. (1).…”

Section: Product State Distributionsmentioning

confidence: 99%

Ultraviolet photodissociation of OCS: Product energy and angular distributions

McBane

Schmidt

Johnson

et al. 2013

The Journal of Chemical Physics

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The ultraviolet photodissociation of carbonyl sulfide (OCS) was studied using three-dimensional potential energy surfaces and both quantum mechanical dynamics calculations and classical trajectory calculations including surface hopping. The transition dipole moment functions used in an earlier study [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] were improved with more extensive treatment of excited electronic states. The new functions indicate a much larger contribution from the 1 1 A state ( 1 − in linear OCS) than was found in the previous work. The new transition dipole functions yield absorption spectra that agree with experimental data just as well as the earlier ones. The previously reported potential energy surfaces were also empirically modified in the region far from linearity. The resulting product state distributions P v,j , angular anisotropy parameters β(j), and carbon monoxide rotational alignment parameters A (2) 0 (j ) agree reasonably well with the experimental results, while those computed from the earlier transition dipole and potential energy functions do not. The higher-j peak in the bimodal rotational distribution is shown to arise from nonadiabatic transitions from state 2 1 A to the OCS ground state late in the dissociation.

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“…13,14 The wavelength dependences of the quantum yields and branching ratios have been determined by dynamics calculations that are based on adiabatic potential energy surfaces that were specifically calculated for these problems 15,16 and on coupling potential terms for non-adiabatic interactions. 17 Another set of issues is associated with the ground state. Its vibrational spectrum presents a challenge in as much as it cannot be accurately recovered by uncorrelated wave functions.…”

Section: Introductionmentioning

confidence: 99%

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

Theis

Ivanic

Windus

et al. 2016

The Journal of Chemical Physics

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The metastable ring structure of the ozone 1 1 A 1 ground state, which theoretical calculations have shown to exist, has so far eluded experimental detection. An accurate prediction for the energy difference between this isomer and the lower open structure is therefore of interest, as is a prediction for the isomerization barrier between them, which results from interactions between the lowest two 1 A 1 states. In the present work, valence correlated energies of the 1 1 A 1 state and the 2 1 A 1 state were calculated at the 1 1 A 1 open minimum, the 1 1 A 1 ring minimum, the transition state between these two minima, the minimum of the 2 1 A 1 state, and the conical intersection between the two states. The geometries were determined at the full-valence multi-configuration self-consistent-field level. Configuration interaction (CI) expansions up to quadruple excitations were calculated with triple-zeta atomic basis sets. The CI expansions based on eight different reference configuration spaces were explored. To obtain some of the quadruple excitation energies, the method of Correlation Energy Extrapolation by Intrinsic Scaling was generalized to the simultaneous extrapolation for two states. This extrapolation method was shown to be very accurate. On the other hand, none of the CI expansions were found to have converged to millihartree (mh) accuracy at the quadruple excitation level. The data suggest that convergence to mh accuracy is probably attained at the sextuple excitation level. On the 1 1 A 1 state, the present calculations yield the estimates of (ring minimum-open minimum) ∼45-50 mh and (transition state-open minimum) ∼85-90 mh. For the (2 1 A 1 -1 A 1 ) excitation energy, the estimate of ∼130-170 mh is found at the open minimum and 270-310 mh at the ring minimum. At the transition state, the difference (2 1 A 1 -1 A 1 ) is found to be between 1 and 10 mh. The geometry of the transition state on the 1 1 A 1 surface and that of the minimum on the 2 1 A 1 surface nearly coincide. More accurate predictions of the energy differences also require CI expansions to at least sextuple excitations with respect to the valence space. For every wave function considered, the omission of the correlations of the 2s oxygen orbitals, which is a widely used approximation, was found to cause errors of about ±10 mh with respect to the energy differences. C 2016 AIP Publishing LLC. [http://dx

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Photodissociation of ozone in the Hartley band: Potential energy surfaces, nonadiabatic couplings, and singlet/triplet branching ratio

Cited by 60 publications

References 67 publications

High spectral resolution ozone absorption cross-sections – Part 1: Measurements, data analysis and comparison with previous measurements around 293 K

High spectral resolution ozone absorption cross-sections – Part 1: Measurements, data analysis and comparison with previous measurements around 293 K

Ultraviolet photodissociation of OCS: Product energy and angular distributions

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

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