Experimental and theoretical studies on Rydberg states of CH2CO in the region 120–220 nm

Chiang, Su‐Yu; Bahou, Mohammed; Wu, Yu Jong; Lee, Yuan‐Pern

doi:10.1063/1.1497630

Cited by 11 publications

(13 citation statements)

References 59 publications

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“…The latter is believed to be too low, in view of the fact that OM2/MRCI underestimates the vertical excitation energy of ketene by ca. 0.7 eV (experimental value: 3.84 eV 114 ).…”

Section: G Ketenementioning

confidence: 99%

Assessment of approximate computational methods for conical intersections and branching plane vectors in organic molecules

Nikiforov

Gámez

Thiel

et al. 2014

The Journal of Chemical Physics

136

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Quantum-chemical computational methods are benchmarked for their ability to describe conical intersections in a series of organic molecules and models of biological chromophores. Reference results for the geometries, relative energies, and branching planes of conical intersections are obtained using ab initio multireference configuration interaction with single and double excitations (MRCISD). They are compared with the results from more approximate methods, namely, the state-interaction state-averaged restricted ensemble-referenced Kohn-Sham method, spin-flip time-dependent density functional theory, and a semiempirical MRCISD approach using an orthogonalization-corrected model. It is demonstrated that these approximate methods reproduce the ab initio reference data very well, with root-mean-square deviations in the optimized geometries of the order of 0.1 Å or less and with reasonable agreement in the computed relative energies. A detailed analysis of the branching plane vectors shows that all currently applied methods yield similar nuclear displacements for escaping the strong non-adiabatic coupling region near the conical intersections. Our comparisons support the use of the tested quantum-chemical methods for modeling the photochemistry of large organic and biological systems. © 2014 AIP Publishing LLC. [http://dx

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“…The latter is believed to be too low, in view of the fact that OM2/MRCI underestimates the vertical excitation energy of ketene by ca. 0.7 eV (experimental value: 3.84 eV 114 ).…”

Section: G Ketenementioning

confidence: 99%

Assessment of approximate computational methods for conical intersections and branching plane vectors in organic molecules

Nikiforov

Gámez

Thiel

et al. 2014

The Journal of Chemical Physics

136

View full text Add to dashboard Cite

show abstract

“… Abstract The absorption spectrum of ketene (CH 2 CO) in the 145‐ to 220‐nm region is calculated completely from first principles and compared to a recent high‐resolution synchrotron radiation experiment J Chem Phys 2002, 117, 4306. The simulations are based on a vibronic model, which is extracted from routinely applicable coupled cluster calculations for electronically excited states.…”

mentioning

confidence: 99%

First‐principles simulation of the UV absorption spectrum of ketene

Nooijen¹

2003

Int J of Quantum Chemistry

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ABSTRACT:The absorption spectrum of ketene (CH 2 ACAO) in the 145-to 220-nm region is calculated completely from first principles and compared to a recent highresolution synchrotron radiation experiment (J Chem Phys 2002, 117, 4306). The simulations are based on a vibronic model, which is extracted from routinely applicable coupled cluster calculations for electronically excited states. Nonadiabatic effects are assessed by a comparison of the vibronic model simulations with Franck-Condon calculations and are found to be important to understand various aspects of the absorption spectrum of ketene.

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“…4 These have been variously assigned to members of both the 3 0 n or 4 0 n progressions ͑n =1-3͒, 5,6 where 3 and 4 are the CH 2 scissor and C v C stretching vibrations, respectively, while a recent comparison of the corresponding features in the ultraviolet absorption spectra of both CH 2 CO and CD 2 CO suggests that the C v O stretching 2 mode is also a major active mode for the ns Rydberg series. 7 Figure 1 shows the vibrational progressions in the absorption spectra with the spectral assignment in Ref. 7.…”

Section: Introductionmentioning

confidence: 99%

“…7 Figure 1 shows the vibrational progressions in the absorption spectra with the spectral assignment in Ref. 7.…”

Section: Introductionmentioning

confidence: 99%

A velocity map ion-imaging study on ketene photodissociation at 208 and 213nm: Rotational dependence of product angular anisotropy

Liu

Wang

et al. 2005

The Journal of Chemical Physics

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Photodissociation dynamics of ketene following excitation at 208.59 and 213.24 nm have been investigated using the velocity map ion-imaging method. Both the angular distribution and translational energy distribution of the CO products at different rotational and vibrational states have been obtained. No significant difference in the translational energy distributions for different CO rotational state products has been observed at both excitation wavelengths. The anisotropy parameter ␤ is, however, noticeably different for different CO rotational state products at both excitation wavelengths. For lower rotational states of the CO product, ␤ is smaller than zero, while ␤ is larger than zero for CO at higher rotational states. The observed rotational dependence of angular anisotropy is interpreted as the dynamical influence of a peculiar conical intersection between the 1 B 1 excited state and 1 A 2 state along the C S -I coordinate.

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Experimental and theoretical studies on Rydberg states of CH2CO in the region 120–220 nm

Cited by 11 publications

References 59 publications

Assessment of approximate computational methods for conical intersections and branching plane vectors in organic molecules

Assessment of approximate computational methods for conical intersections and branching plane vectors in organic molecules

First‐principles simulation of the UV absorption spectrum of ketene

A velocity map ion-imaging study on ketene photodissociation at 208 and 213nm: Rotational dependence of product angular anisotropy

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