Dispersed fluorescence studies of linear LiOLi: a strongly bound, but very `floppy' ionic molecule

Bellert, D.; Winn, Darin K.; Breckenridge, W. H.

doi:10.1016/s0009-2614(01)00996-4

Cited by 14 publications

(11 citation statements)

References 12 publications

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“…2 All of the 54 DF bands definitively recorded can now be consistently assigned, with resulting experimental vibrational constants which are astoundingly close to the very recent ab initio values. 7 ͑See Table II.͒ A few DF spectra recorded for the much less abundant 6 Li 16 O 7 Li isotope ͑signal-to-noise was thus much lower͒ were consistent with the assignments in Table I.…”

Section: Shown Insupporting

confidence: 72%

“…It should be noted that preliminary assignments 2 of a few weak bands as being due to transitions to ( 1 Љ , 2 Љ , 3 Љϭ2) levels, although qualitatively reasonable at the time given the DF data from one 1 B 1 upper-state vibrational level only, 2 have proved to be unsatisfactory as we recorded many more bands from other upper states which could not be fit adequately with the constants derived from that preliminary assignment. 2 All of the 54 DF bands definitively recorded can now be consistently assigned, with resulting experimental vibrational constants which are astoundingly close to the very recent ab initio values.…”

Section: Shown Inmentioning

confidence: 71%

“…Because only KЈ ϭ1 states are created in this perpendicular excitation, only 2 Љ lower levels with g ϩ or ␦ g symmetry ͓vibrational angular momentum states lЉϭ0 or 2 of LiOLi͓ 1 ⌺ g ϩ ͔͔ can be reached by allowed ͑perpendicular͒ fluorescence transitions (KЈϪlЉ ϭϮ1). 2 was insufficient to resolve the separate transitions to the g ϩ and ␦ g vibrational angular momentum levels of the 2 Љу2…”

Section: A Dispersed Fluorescence Spectramentioning

confidence: 99%

“…[1][2][3][4] Here, we describe more extensive dispersed fluorescence ͑DF͒ experiments and new stimulated emission pumping ͑SEP͒ experiments which have provided a great deal of information about the lowlying rovibronic levels of the LiOLi ground state. The rotationally resolved SEP experiments confirm the results of early electric field deflection experiments 5 of Klemperer and co-workers ͑as well as those of recent high-level ab initio calculations 6-8 ͒: the LiOLi molecule is linear.…”

Section: Introductionmentioning

confidence: 99%

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Rovibrational energy levels of the LiOLi molecule from dispersed fluorescence and stimulated emission pumping studies

Bellert

Winn

Breckenridge

2002

The Journal of Chemical Physics

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Articles you may be interested inExperimental observation and analysis of the 3ν1(Σg) stretching vibrational state of acetylene using continuouswave infrared stimulated emission J. Chem. Phys. 139, 054201 (2013); 10.1063/1.4816524The rotational spectrum and dynamical structure of LiOH and LiOD: A combined laboratory and ab initio study A spectroscopic determination of the bond length of the LiOLi molecule: Strong ionic bonding Rotational coherence spectroscopy of para-cyclohexylaniline by stimulated Raman-induced fluorescence depletion and stimulated emission pumping Dispersed fluorescence ͑DF͒ and stimulated emission pumping ͑SEP͒ experiments have been carried out on the jet-cooled 7 Li 16 O 7 Li molecule. Rotationally resolved SEP bands to 2 l (lϭ0,2) vibrational angular momentum levels show that LiOLi is a linear molecule. The DF experiments have resulted in the measurement of 54 ( 1 , 2 l ,0) levels of the X 1 ⌺ g ϩ ground state, up to 6000 cm Ϫ1 . The energy levels determined experimentally are amazingly close to those calculated very recently for a high-level ab initio LiOLi(X 1 ⌺ g ϩ ) potential surface. The DF vibrational level energies are analyzed and discussed in terms of a global fit to an 11-term power series. From the SEP experiments, effective rotational constants B 1 , 2 l ,0 for several of these vibrational levels ͓including g ϩ (lϭ0) and␦ g (lϭ2) vibrational angular momentum states for ( 1 , 2 l у2(even), 3 ϭ0) levels͔ have also been determined. The bond distance R 0 is estimated to be 1.611Ϯ0.003 Å from an extrapolation of B 1 ,0,0 values. Finally, the unusual ''Li ϩ O Ϫ2 Li ϩ '' ionic bonding and the low 2 ϭ112 cm Ϫ1 bending frequency for LiOLi(X 1 ⌺ g ϩ ) are briefly discussed.

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Section: Shown Insupporting

confidence: 72%

Section: Shown Inmentioning

confidence: 71%

Section: A Dispersed Fluorescence Spectramentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Rovibrational energy levels of the LiOLi molecule from dispersed fluorescence and stimulated emission pumping studies

Bellert

Winn

Breckenridge

2002

The Journal of Chemical Physics

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“…[1][2][3][4] The LiOLi ground state, unlike its valence isoelectronic HOH analogue, has been shown in SEP ͑stimulated emission pumping͒ experiments to be linear, with a bond length (R 0,0,0 Љ ) of 1.611Ϯ0.003 Å. 4 Here, we describe extensive laser-induced fluorescence ͑LIF͒ and resonance-enhanced two-photon ionization ͑R2PI͒ measurements in which we have determined the rotational energy levels of several excited ( 1 Ј , 2 Ј , 3 Ј) vibrational states of the Ã 1 B 1 (KЈϭ1) electronically excited state of 7 Li 16 O 7 Li.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic characterization of the first singlet (Ã B11) excited state of Li167O7Li

Bellert¹,

Winn²,

Breckenridge³

2003

The Journal of Chemical Physics

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Using laser induced fluorescence (LIF) and resonance enhanced two-photon ionization (R2PI) spectroscopy, several (ν1′,ν2′,ν3′) vibrational bands of the Ã 1B1(K′=1)←X̃ 1Σg+(0,0,0) perpendicular transition of the Li167O7Li molecule have been rotationally resolved and analyzed to yield effective A′,B′,C′ values. The estimated geometry of the Ã 1B1 state does not vary with ν1′ (symmetric stretch mode), but θ′ increases and R′ decreases slightly as ν2′ (bending mode) increases. Extrapolation leads to an estimate for the (0,0,0) state of θ0′=105±5°, R0′=1.86±0.04 Å, and for the potential minimum θe′=102±5°, Re′=1.87±0.04 Å. The strongly bent nature of the Ã 1B1 state is due to promotion of an O−2 p-electron (b1) from the strongly ionic, linear Li+O−2Li+ ground state to an a1 molecular orbital which has Li/Li bonding character. The Ã 1B1 state thus has an approximately Li+1/2O−1Li+1/2 charge distribution, so that the ionic bonding is less strong than in the linear ground state, where (from this study and an earlier stimulation-emission pumping study) R0″=1.611±0.003 Å. In fact, the Li–Li distance in the Ã 1B1 state, ∼3.0 Å, is quite similar to that of the Li2+1 ion, so the bonding may be described as that of Li2+1 bound ionically to the O−1 ion.

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120 Li2O (LiOLi)

Guelachvili

2008

Linear Triatomic Molecules

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Dispersed fluorescence studies of linear LiOLi: a strongly bound, but very `floppy' ionic molecule

Cited by 14 publications

References 12 publications

Rovibrational energy levels of the LiOLi molecule from dispersed fluorescence and stimulated emission pumping studies

Rovibrational energy levels of the LiOLi molecule from dispersed fluorescence and stimulated emission pumping studies

Spectroscopic characterization of the first singlet (Ã B11) excited state of Li167O7Li

120 Li2O (LiOLi)

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