Spectroscopic determination of the vibrational frequencies of the first 1B1 excited state of LiOLi

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

doi:10.1016/s0009-2614(02)00201-4

Cited by 5 publications

(5 citation statements)

References 9 publications

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“…Ј , as expected for a fairly harmonic symmetric-stretch potential ( 1 Јϭ601; 11 Ј ϭϪ3.1) 3. From the RЈ values extrapo-…”

supporting

confidence: 77%

“…As above, since there is no obvious trend in AЈ,BЈ,CЈ,RЈ,Ј values in the ͑4,1,0͒, ͑3,1,0͒, ͑2,1,0͒ progression, we assume extrapolation to 1 Ј ϭϪ1/2 ͑and to 3 ЈϭϪ1/2 as well͒ will cause no change in AЈ,BЈ,CЈ, so that the only changes which will occur is in the extrapolation to 2 ЈϭϪ1/2. ͑We also assume, of course, that the geometries of the KЈϭ1 levels are essentially identical to the KЈϭ0 states.͒ We thus estimate the AЈ,BЈ,CЈ values ͑for 1 ЈϭϪ1/2; 2 ЈϭϪ1/2; 3 ЈϭϪ1/2) to be ͑see 3 …”

Section: Estimate Of the Geometry Of Lioli"ã 1 B 1 … At The Potentmentioning

confidence: 99%

“…[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%

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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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“…Ј , as expected for a fairly harmonic symmetric-stretch potential ( 1 Јϭ601; 11 Ј ϭϪ3.1) 3. From the RЈ values extrapo-…”

supporting

confidence: 77%

Section: Estimate Of the Geometry Of Lioli"ã 1 B 1 … At The Potentmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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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“…͑See below for SEP results which confirm our assignments, however.͒ These assignments also result in a 2 Љ harmonic frequency of 111.6Ϯ0.4 cm Ϫ1 , consistent with the fundamental bending frequency of 112 cm Ϫ1 found in a matrix isolation study. 11 We have carefully collected similar DF spectra from nine different ( 1 Ју2; 2 Ј ; 3 Ј) vibrational levels 3 Table I are the mean energies of all the assigned lower ( 1 Љ , 2 Љ , 3 Љ) levels ͑for all such spectra͒ relative to the ͑0,0,0͒ level, with estimated uncertainties ͑standard deviations of the mean of all determinations of the relative energy of that level͒. This global data set was also fit to an 11-term power series…”

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%

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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120 Li2O (LiOLi)

Guelachvili

2008

Linear Triatomic Molecules

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Spectroscopic determination of the vibrational frequencies of the first 1B1 excited state of LiOLi

Cited by 5 publications

References 9 publications

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

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

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

120 Li2O (LiOLi)

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