The boron K photoabsorption spectra of BF3, BCl3, and BBr3

Ishiguro, Eiji; Iwata, Suehiro; Suzuki, Y; Mikuni, Akira; Sasaki, Takehiko

doi:10.1088/0022-3700/15/12/008

Cited by 62 publications

(32 citation statements)

References 17 publications

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“…Using the vertical IP of 12.66 eV as the convergence limit we calculate an effective quantum number (n*) for this state of 1.97. (It is also observed weakly in the inner shell absorption spectrum, where the B ls ~ ~* (3a~1)/3s transition occurs at 196.1 eV, with an n* value of 1.92 [29].) This state is equivalent to the (3e~) -I 3s state of BF 3 at 13.1 eV [1,26], and we note that in both BF 3 and BCI3 it is broadened with no underlying vibrational structure.…”

Section: Assignment Of the Rydberg Transitions In Bci3mentioning

confidence: 61%

Vacuum UV fluorescence excitation spectroscopy of BCl₃in the range 35–140 nm

et al. 1993

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Fluorescence excitation spectra of BC13 have been recorded in the range 35-140 nm (9-35 eV) using synchrotron radiation. Both resonant and non-resonant peaks are observed corresponding to neutral fragment (i.e. BC12) and parent ion (i.e. BC1 +) emission. BC12 emission results from dissociation of low-lying Rydberg states of BC13 in the energy range 9-12 eV, and at least two electronic transitions in BC12 are observed. One (in the range 400-650 nm) originates from dissociation of the 3s and 3p Rydberg states, whilst the other (in the range 250-500 nm) originates from higher members of the s, p and d Rydberg series. The emitting states in BC1 + are the I3 2E' and 1~ 2A] states with adiabatic ionization potentials of 15'3 and 17"7eV. The results are compared with vacuum UV absorption studies of BCI3, and with similar experiments on BF 3 which lead to fluorescence processes in BF 2 and BF~-.

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Section: Assignment Of the Rydberg Transitions In Bci3mentioning

confidence: 61%

Vacuum UV fluorescence excitation spectroscopy of BCl₃in the range 35–140 nm

et al. 1993

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“…Similar difficulties appear in the interpretation of the x-ray [6] and uv [25] absorption spectra of BC13. Although both MS-XCI ( Table I) and HF methods give reasonable B 1s XAS term energies and intensities for BF, , both methods have problems with the apparent 4e' feature in the spectrum of BC13, giving term energies and relative oscillator strengths that are too small.…”

Section: Resultsmentioning

confidence: 89%

“…These discrepancies may arise either from a poor description of the 4e' orbital or from vibronically allowed intensity to the 3aI orbital, which is quite localized in BCI3 as we have indicated. It has been argued that vibrationally excited BX3 molecules will be nonplanar with C3" symmetry, so that the Bls(a;) --$ 3aI transition is allowed [6]. Since the frequency of the out-of-plane a;' vibration of BC13 is one-third smaller than that of BF3 [27], we expect such vibronic coupling effects to be larger in BC1,.…”

Section: Resultsmentioning

confidence: 91%

Studies of unoccupied orbitals of BF₃ and BCL₃ by electron transmission spectroscopy and multiple scattering Xα calculations

Tossell

Moore

Olthoff

1986

Int J of Quantum Chemistry

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Electron transmission spectroscopy (ETS) and bound-state and continuum multiple-scattering X a (MS-Xa) calculations are employed to characterize the unoccupied a;, a; and e' orbitals of BF, and BCI,. The a; orbital of BF,, which produces a peak about 7 eV below threshold in the x-ray absorption spectrum (XAS), generates a scattering resonance at 3.5 eV in ETS. Similarly, the e' orbital that lies about 2 eV above threshold in XAS occurs about 13-16 eV above threshold in ETS. Dissociation of F-from BF, due to electron attachment is attributed to a core-excited shape resonance involving an e" 4 a; excitation and electron capture into the a; orbital. In BCI, all the unoccupied orbitals lie at lower energy than in BF, and are closely spaced, making definitive spectral assignments difficult. Both Hartree-Fock (HF) and M S -X~ methods apparently underestimate the stability of the unoccupied e' orbital of BCI,. Vibronic coupling due to out-of-plane bending may significantly affect the spectral intensities. Feshbach resonances are observed for BCI, at energies close. to those observed in the vacuum-uv absorption spectrum. The lower energies of the unoccupied orbitals of BCI, are consistent with their stronger bonding to nucleophiles.

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“…That is, the IsB + cr* excitation in BF, is at higher frequency than the 1sB-I ionization potential (by 18 500 cm-I), and consequently appears as a shape resonance (7). There is a strong possibility that the outer shell A(2pF,u*) band of BF, also will lie above the 2pF-' ionization limit.…”

Section: Ib Term-value Trends and Bond Strengthsmentioning

confidence: 99%

Antibonding σ* orbitals in molecular spectroscopy

Robin¹

1985

Can. J. Chem.

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This paper is dedicated to Professor Camille Sandorfy on the occasion of his 65th birthdayM. B. ROBIN. Can. J . Chem. 63, 2032Chem. 63, (1985. This paper discusses the role of a* antibonding valence MO's in the electronic spectra of large molecules. Using the term value and antishielding concepts, molecular absorption patterns terminating at a* MO's are systematized and rationalized; the frequencies of such excitations correlate with the ground-state bond strengths of the bonds giving rise to the a* MO's. In unsaturated systems, the 7~ + a* and np + a* excitations can be distinguished on the basis of their term values. Confusion in the past regarding the existence of excitations to a* relates to the fact that a* MO's often can be totally mixed into the surrounding sea of Rydberg levels of the same symmetry, and for all practical purposes can cease to exist except as perturbations on the Rydberg levels. For nonpenetrating Rydberg manifolds there is little or no mixing with a* MO's of the same symmetry, setting the stage for the appearance of valence-shell excitations to a* in high-symmetry molecules which are analogous to the d + f inner-well giant resonances of atomic spectroscopy.M. B. ROBIN. Can. J. Chem. 63, 2032Chem. 63, (1985. Dans ce travail, on discute du r61e des OM de valence antiliante a* dans les spectres Clectroniques des grosses molCcules. Utilisant les concepts de valeur de terme et d'antiblindage, on systimatise et on rationalise les types d'absorptions molCculaires qui se terminent au niveau des OM a*; il existe une correlation entre les frCquences de telles excitations et les longueurs de liaisons dans I'Ctat atomique fondamental qui donne lieu aux OM a*. Dans les systkmes non-saturCs, on peut distinguer les excitations 7~ + a* des excitations np + a* en se basant sur leurs valeurs de terme. La confusion qui a Ct C observte dans le passe relativement a I'existence d'excitations vers les niveaux a* provient du fait que les OM u* peuvent souvent Ctre complktement confondues avec les niveaux de Rydberg de m&me symCtrie qui les entourent et, a toutes fins pratiques, elles cessent d'exister, except6 comme perturbations des niveaux de Rydberg. Pour les Ctats non-pCnCtrants de Rydberg, il y peu ou pas du tout de mtlange avec les OM a* de mCme symCtrie et ceci permet, dans les molCcules de haute symCtrie, de noter ]'apparition d'excitations des couches de valence vers les Ctats a* qui sont semblables aux rksonances @antes d + f de la spectroscopie atomique.[Traduit par le journal]

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The boron K photoabsorption spectra of BF₃, BCl₃, and BBr₃

Cited by 62 publications

References 17 publications

Vacuum UV fluorescence excitation spectroscopy of BCl₃in the range 35–140 nm

Vacuum UV fluorescence excitation spectroscopy of BCl₃in the range 35–140 nm

Studies of unoccupied orbitals of BF₃ and BCL₃ by electron transmission spectroscopy and multiple scattering Xα calculations

Antibonding σ* orbitals in molecular spectroscopy

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The boron K photoabsorption spectra of BF3, BCl3, and BBr3

Cited by 62 publications

References 17 publications

Vacuum UV fluorescence excitation spectroscopy of BCl3in the range 35–140 nm

Vacuum UV fluorescence excitation spectroscopy of BCl3in the range 35–140 nm

Studies of unoccupied orbitals of BF3 and BCL3 by electron transmission spectroscopy and multiple scattering Xα calculations

Antibonding σ* orbitals in molecular spectroscopy

Contact Info

Product

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The boron K photoabsorption spectra of BF₃, BCl₃, and BBr₃

Vacuum UV fluorescence excitation spectroscopy of BCl₃in the range 35–140 nm

Vacuum UV fluorescence excitation spectroscopy of BCl₃in the range 35–140 nm

Studies of unoccupied orbitals of BF₃ and BCL₃ by electron transmission spectroscopy and multiple scattering Xα calculations