The electronic states of cyclopropane studied by VUV absorption and<i>ab initio</i>multireference configuration interaction calculations

Walker, Isobel C.; Holland, D.M.P.; Shaw, David; McEwen, I.J.; Guest, Martyn F.

doi:10.1088/0953-4075/40/10/021

Cited by 9 publications

(13 citation statements)

References 34 publications

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“…Interestingly, the term value (∼1.7 eV) for this π →π * transition in the valence shell of pyrimidine is several eV smaller than that (∼6 eV) observed for the corresponding N 1s excitation into the 2a 2 (π * ) orbital [13]. This shift of a few eV is as expected when comparing the term values for valence and core level excitations [51]. In the experimental spectrum (figure 6), the region between ∼8 and 10 eV displays extensive vibrational structure ascribed to Rydberg series converging onto the (7b 2 ) −1 X 2 B 2 ionization limit at 9.331 eV [19].…”

Section: Valence Transitions In Pyrimidinesupporting

confidence: 50%

“…Structure due to Rydberg transitions is weak and it is apparent that excitations into valence states provide the major contributions to the photoabsorption cross sections. In both pyrimidine and pyrazine the photoabsorption spectrum exhibits a broad maximum at ∼20 eV, as is typical in absorption spectra of three [51], five [52,53] and six [8,9,54] membered ring-type molecules. The absolute values of the cross sections obtained in the present work are slightly greater than those measured previously [5,7].…”

Section: Overview Of the Total Photoabsorption Spectra Of Pyrimidine ...mentioning

confidence: 61%

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A study of the valence shell electronic states of pyrimidine and pyrazine by photoabsorption spectroscopy and time-dependent density functional theory calculations

Stener

Decleva

Holland

et al. 2011

J. Phys. B: At. Mol. Opt. Phys.

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The valence shell electronic states of pyrimidine and pyrazine have been studied experimentally and theoretically. The absolute photoabsorption cross sections have been measured between 4 and 40 eV, using synchrotron radiation, and are dominated by prominent bands associated with intravalence transitions. In contrast, the structure due to Rydberg excitations is weak, but series have been observed converging onto the X 2 B 2 or D 2 B 1 limits in pyrimidine and the X 2 A g or D 2 B 3g limits in pyrazine. A comparison between the photoabsorption spectrum of pyrazine-h 4 and that for pyrazine-d 4 , together with calculated transition energies, has helped clarify the assignments of the 6a g →npb 1u and npb 2u Rydberg series. The vibrational progressions associated with these states have been assigned through analogy with those in the corresponding photoelectron band. The time-dependent version of density functional theory has been used to calculate oscillator strengths and excitation energies for the optically allowed singlet-singlet valence transitions, and also to obtain the excitation energies for electric-dipole-forbidden and/or spin-forbidden transitions. These theoretical results have allowed many of the experimentally observed bands to be assigned and provide a generally satisfactory description of the valence shell photoabsorption spectrum. Several of the prominent bands appearing above the ionization threshold can be correlated with predicted intense intravalence transitions.

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Section: Valence Transitions In Pyrimidinesupporting

confidence: 50%

Section: Overview Of the Total Photoabsorption Spectra Of Pyrimidine ...mentioning

confidence: 61%

A study of the valence shell electronic states of pyrimidine and pyrazine by photoabsorption spectroscopy and time-dependent density functional theory calculations

Stener

Decleva

Holland

et al. 2011

J. Phys. B: At. Mol. Opt. Phys.

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“…This has extended our understanding of both Rydberg and valence-excited states. The work follows similar studies on cyclopropane (Walker et al 2007) and ethylene sulphide (Holland et al 2008).…”

Section: Introductionmentioning

confidence: 70%

The electronic states of ethylene oxide studied by photoabsorption andab initiomultireference configuration interaction calculations

Walker¹,

Holland²,

Shaw³

et al. 2008

J. Phys. B: At. Mol. Opt. Phys.

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The absolute photoabsorption spectrum of ethylene oxide (C2H4O) has been measured between onset and 30 eV, using monochromated synchrotron radiation. Below the ionization threshold (10.56 eV) the spectrum is dominated by sharp peaks related to excitation of Rydberg series converging on the first ionization energy. Above the ionization threshold, valence-excited states, which give rise to broad bands, predominate. Underlying Rydberg states are signalled in weak vibrational structure on the valence bands. Ab initio multireference configuration interaction (MRDCI) calculations have been carried out to assist in assignment of the excited states, both valence and Rydberg. The lowest-lying valence state is electric-dipole forbidden; the first optically allowed valence state lies close to the ionization onset. The spectrum of the oxide is compared with those of cyclopropane (C3H6) and ethylene sulphide (C2H4S).

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“…The two lowest-lying dipole allowed absorption bands with significant oscillator strength have their onset at 7.1 eV and exhibit broad maxima centered at 7.9 and 8.6 eV. 21,22 These two bands were attributed to the two Jahn-Teller (JT) split components of the E (σ3p x/y ) state. Previous assignments of the absorption spectrum have, however, neglected the effects of vibronic coupling.…”

Section: Introductionmentioning

confidence: 99%

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

Coates

Larsen

Forbes

et al. 2018

The Journal of Chemical Physics

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The vacuum-ultraviolet photoinduced dynamics of cyclopropane (C 3 H 6) were studied using timeresolved photoelectron spectroscopy (TRPES) in conjunction with ab initio quantum dynamics simulations. Following excitation at 160.8 nm, and subsequent probing via photoionization at 266.45 nm, the initially prepared wave packet is found to exhibit a fast decay (<100 fs) that is attributed to the rapid dissociation of C 3 H 6 to ethylene (C 2 H 4) and methylene (CH 2). The photodissociation process proceeds via concerted ring opening and CC bond cleavage in the excited state. Ab initio multiple spawning simulations indicate that ring-opening occurs prior to dissociation. The dynamics simulations were subsequently employed to simulate a TRPES spectrum, which was found to be in excellent agreement with the experimental result. On the basis of this agreement, the fitted time constants of 35 ± 20 and 57 ± 35 fs were assigned to prompt (i) dissociation on the lowest-lying excited state, prepared directly by the pump pulse, and (ii) non-adiabatic relaxation from higher-lying excited states that lead to delayed dissociation, respectively.

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The electronic states of cyclopropane studied by VUV absorption andab initiomultireference configuration interaction calculations

Cited by 9 publications

References 34 publications

A study of the valence shell electronic states of pyrimidine and pyrazine by photoabsorption spectroscopy and time-dependent density functional theory calculations

A study of the valence shell electronic states of pyrimidine and pyrazine by photoabsorption spectroscopy and time-dependent density functional theory calculations

The electronic states of ethylene oxide studied by photoabsorption andab initiomultireference configuration interaction calculations

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

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