Fine and Hyperfine Structure in the Vibrational Spectrum of the X2Π State of HBr+

Chanda, A.; Ho, Wing-Chung; Dalby, F. W.; Ozier, I.

doi:10.1006/jmsp.1995.1009

Cited by 9 publications

(20 citation statements)

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“…Within the error limits this value for p is in agreement with numbers reported by Norling 13 and Barrow et al, 14 who applied the same formula. It is also compatible with values reported by Lubic et al 22 and Chanda et al 23 In the 2 Π 3/2 state the Λ-doubling is too small to be measured accurately in our experiment (<0.1 cm -1 ) for the given rotational states. Therefore we did not attempt to derive a value for the second Λ-doubling constant q.…”

Section: Preparation Of Hbr + Via the 2+1 Rempi Processsupporting

confidence: 93%

State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr⁺) via the ²Σ⁺ ← ²Π_i(i=1/2, 3/2) Transition

1998

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The photodissociation of hydrogen bromide ions (HBr + ) has been investigated via the 2 Σ + (V′)1, 2, 3, and 4) r 2 Π i (i)1/2, 3/2, V′′)0) transitions. The spectra reveal that state selective photodissociation with complete resolution of the rotational, orbital, and spin angular momentum as well as the parity of the HBr + ions is possible in the 2 Σ + (V′)1, 2). The analysis of the spectra yields the rotational constants, the spin-rotation coupling constant, and the orbit-rotation coupling constant in the respective electronic states. All angular momentum eigenstates of the 2 Σ + (V′)2) state (and of all higher vibrational states) predissociate. The first eigenstate in the 2 Σ + (V′)1) state that predissociates is the J′ ) 25/2, R′ ) 12 state. The lifetime of HBr + is found to decrease significantly with increasing vibrational excitation in the 2 Σ + state. Within the experimental error limits no J dependence of the lifetime is observed.

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Section: Preparation Of Hbr + Via the 2+1 Rempi Processsupporting

confidence: 93%

State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr⁺) via the ²Σ⁺ ← ²Π_i(i=1/2, 3/2) Transition

1998

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“…The positions of the vibrational fundamentals of ground-state HBr ϩ and DBr ϩ were determined some time ago by emission spectroscopy, 7 and recently the high resolution gas-phase infrared spectrum of HBr ϩ was observed and analyzed in detail. 8 The positions of the vibrational fundamentals of H 2 Br ϩ and D 2 Br ϩ were derived from ab initio calculations by Botschwina and co-workers. 9 However, no vibrational data have been reported for ͑HBr͒ 2 ϩ .…”

Section: Introductionmentioning

confidence: 99%

The vibrational spectra of molecular ions isolated in solid neon. XIII. Ions derived from HBr and HI

Lugez

Jacox

Thompson

1996

The Journal of Chemical Physics

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Articles you may be interested inOn the vibrational fine structure in the nearthreshold photofragmentation spectrum of the I−CH3I complex: Spectroscopic observation of nonadiabatic effects in electronmolecule scattering When a Ne:HBr or a Ne:HI sample is codeposited at approximately 5 K with discharge-excited neon atoms, the infrared spectrum of the resulting solid includes not only the absorptions of the HX molecule and its multimers but also a prominent absorption of HBr ϩ or HI ϩ . The absorption of each of the two cations lies within a few cm Ϫ1 of its gas-phase band center. The vibrational fundamentals of DBr ϩ and DI ϩ are also identified in experiments on deuterium-enriched samples. Other infrared absorptions are assigned to normal and deuterium-substituted ͑HBr͒ 2 ϩ and ͑HI͒ 2 ϩ , as well as to BrHBr Ϫ , BrDBr Ϫ , and IHI Ϫ . Studies of changes in the absorption spectrum following exposure of the deposit to filtered visible and near ultraviolet radiation support these assignments and provide further information on photodissociation and photodetachment processes occurring in these systems.

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“…Second, we elucidate the important role of the chemical bond in enhancement of electron EDM in molecular systems. While both HBr and HI ions have a similar electronic structure, the chemical bond in HBr is of ionic nature, while for heavier HI it is predominantly covalent [11,12]. We find that this evolution in the character of the chemical bond has a marked effect on the EDM-induced energy corrections.…”

mentioning

confidence: 76%

“…As a reference, here we also present the DHF value for the HI ion in the ionic bond approximation, W d HI ; ionic; DHF; X 2 3=2 ÿ7:0 10 ÿ2 d e : (11) Covalent bond approximation for HI .-From the preceding discussion it is clear that a participation of the unpaired p 1=2 or s 1=2 orbital in the ground-state configuration of the heavier molecular constituent is important for gaining a large W d parameter. Qualitatively we can hope that such an enhancement for the X 2 3=2 component may arise when the chemical bond acquires a covalent character (case of the HI ion).…”

mentioning

confidence: 99%

Marked Influence of the Nature of the Chemical Bond onCP-Violating Signature in Molecular IonsHBr+and
Ravaine
¹
,
Porsev
²
,
Derevianko
³

2005
Phys. Rev. Lett.

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Heavy polar molecules offer a great sensitivity to the electron electric dipole moment (EDM). To guide emerging searches for EDMs with molecular ions, we estimate the EDM-induced energy corrections for hydrogen halide ions HBr(+) and HI(+) in their respective ground X (2)Pi(3/2) states. We find that the energy corrections due to EDM for the two ions differ by an unexpectedly large factor of 15. We demonstrate that a major part of this enhancement is due to a dissimilarity in the nature of the chemical bond for the two ions: the bond that is nearly of ionic character in HBr(+) exhibits predominantly a covalent nature in HI(+). We conclude that because of this enhancement the HI(+) ion may be a potentially competitive candidate for the EDM search.

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Fine and Hyperfine Structure in the Vibrational Spectrum of the X2Π State of HBr+

Cited by 9 publications

References 0 publications

State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr⁺) via the ²Σ⁺ ← ²Π_i(i=1/2, 3/2) Transition

State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr⁺) via the ²Σ⁺ ← ²Π_i(i=1/2, 3/2) Transition

The vibrational spectra of molecular ions isolated in solid neon. XIII. Ions derived from HBr and HI

Marked Influence of the Nature of the Chemical Bond onCP-Violating Signature in Molecular IonsHBr+and
Ravaine
¹
,
Porsev
²
,
Derevianko
³

2005
Phys. Rev. Lett.

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Fine and Hyperfine Structure in the Vibrational Spectrum of the X2Π State of HBr+

Cited by 9 publications

References 0 publications

State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr+) via the 2Σ+ ← 2Πi(i=1/2, 3/2) Transition

State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr+) via the 2Σ+ ← 2Πi(i=1/2, 3/2) Transition

The vibrational spectra of molecular ions isolated in solid neon. XIII. Ions derived from HBr and HI

Marked Influence of the Nature of the Chemical Bond onCP-Violating Signature in Molecular IonsHBr+andRavaine1, Porsev2, Derevianko3 2005Phys. Rev. Lett.

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State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr⁺) via the ²Σ⁺ ← ²Π_i(i=1/2, 3/2) Transition

State Selective Predissociation Spectroscopy of Hydrogen Bromide Ions (HBr⁺) via the ²Σ⁺ ← ²Π_i(i=1/2, 3/2) Transition

Marked Influence of the Nature of the Chemical Bond onCP-Violating Signature in Molecular IonsHBr+and
Ravaine
¹
,
Porsev
²
,
Derevianko
³

2005
Phys. Rev. Lett.