FTIR spectrum of benzene in a supersonic expansion

Snavely, D. L.; Walters, Valerie A.; Colson, Steven D.; Wiberg, Kenneth B.

doi:10.1016/0009-2614(84)80333-4

Cited by 44 publications

(19 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These bands occur at 3048, 3079, and 3101 cm -1 in the gas phase. 40 It is apparent from the band positions and their intensities that the liquid benzene spectrum is essentially reproduced as the multiplet observed for the n ) 3 and 4 complexes. In addition to the features at 3086 (n ) 3) or 3085 (n ) 4) cm -1 corresponding to the 3088 cm -1 band in the smaller clusters, the multiplets have bands at 3043, 3073, and 3096 cm -1 (n ) 3) or 3043, 3074, and 3096 cm -1 (n ) 4), all of which are within 4-6 cm -1 of corresponding bands in the liquid spectrum.…”

Section: Resultsmentioning

confidence: 90%

Structure, Coordination, and Solvation of V⁺(benzene)_n Complexes via Gas Phase Infrared Spectroscopy

2004

View full text Add to dashboard Cite

V+(C6H6) n (n = 1−4) and V+(C6H6) n Ar (n = 1, 2) complexes are produced by laser vaporization in a pulsed nozzle cluster source. The clusters are mass-selected and studied by infrared laser photodissociation spectroscopy in the C−H stretch region of benzene. Photodissociation of V+(C6H6) n complexes occurs by the elimination of intact neutral benzene molecules, whereas V+(C6H6) n Ar complexes lose Ar. The dissociation process is enhanced on vibrational resonances and the spectrum is obtained by monitoring fragment yield versus the infrared wavelength. Vibrational bands in the 2700−3300 cm-1 region are characteristic of the benzene molecular moiety with systematic shifts caused by the metal bonding. A dramatic change in the IR spectrum occurs at n = 3, confirming that two ligands complete the coordination sphere and that additional benzenes act as solvent. The comparison between experiment and theory provides fascinating new insight into the bonding in these prototypical organometallic complexes.

show abstract

Section: Resultsmentioning

confidence: 90%

Structure, Coordination, and Solvation of V⁺(benzene)_n Complexes via Gas Phase Infrared Spectroscopy

2004

View full text Add to dashboard Cite

show abstract

“…At the BPW91-D2 level of theory, the C–H stretching band for benzene is placed at 3114 cm –1 , differing from the experimental value of 3047.3 cm –1 for the fundamental C–H stretch of this molecule. , Thus, a scaling factor of 0.98 (≈3047.3/3114) was employed for the C–H stretching frequencies of Ni + (C 6 H 6 ) m . The scaled values are used for the analysis of the IR spectra.…”

Section: Results and Discussionmentioning

confidence: 99%

Theoretical Study of Nascent Solvation in Ni⁺(Benzene)_m, m = 3 and 4, Clusters

2013

View full text Add to dashboard Cite

The ligand versus solvent behavior of Ni(+)(C6H6)3,4 complexes was studied using density functional theory all-electron calculations. Dispersion corrections were included with the BPW91-D2 method using the 6-311++G(2d,2p) basis set. The ground state (GS) for Ni(+)(C6H6)3 has three benzene rings 3d-π bonded to the metal. A two-layer isomer with two moieties coordinated η(3)-η(2) with Ni(+), and the other one adsorbed by van der Waals interactions to the Ni(+)(C6H6)2 subcluster, i.e., a 2 + 1 structure, is within about 8.4 kJ/mol of the GS. Structures with 3 + 1 and 2 + 2 ligand coordination were found for Ni(+)(C6H6)4. The binding energies (D0) of 28.9 and 26.0 kJ/mol for the external moieties of Ni(+)(C6H6)3,4 are much smaller than that for Ni(+)(C6H6)2, 193.0 kJ/mol, obtained also with BPW91-D2. This last D0 overestimates somehow the experimental value, of 146.7 ± 11.6 kJ/mol, for Ni(+)(C6H6)2. The abrupt fall for D0(Ni(+)(C6H6)3,4) shows that such molecules are bound externally as solvent species. These results agree with the D0(Ni(+)(C6H6)3) < 37.1 kJ/mol limit found experimentally for this kind of two-layer clusters. The ionization energies also decrease for m = 2, 3, and 4 (580.8, 573.1, and 558.6 kJ/mol). For Ni(+)(C6H6)3,4, each solvent moiety bridges the benzenes of Ni(+)(C6H6)2; their position and that of one internal ring mimics the tilted T-shape geometry of the benzene dimer (Bz2). The distances from the center of the external to the center of the internal rings for m = 3 (4.686 Å) and m = 4 (4.523 Å) are shorter than that for Bz2 (4.850 Å). This and charge transfer effects promote the (C(δ-)-H(δ+))(int) dipole-π(ext) interactions in Ni(+)(C6H6)3,4; π-π interactions also occur. The predicted IR spectra, having multiplet structure in the C-H region, provide insight into the experimental spectra of these ions.

show abstract

“…20,21 These spectroscopic experiments have been accompanied by harmonic force field parameterizations of successively increasing accuracy and sophistication. A prototypical, empirical fit by Whiffen7 has been improved upon by Duinker and Mills, 8 Kydd,9 and lately Ozkabak et al3 However, the ab initio calculation by Pulay, Fogarasi, and Boggs1 does not predict the force constants which have been deduced from the empirical fits to experimental data.…”

mentioning

confidence: 99%

Infrared–ultraviolet double resonance studies of benzene molecules in a supersonic beam

Page¹,

Shen²,

Lee³

1988

The Journal of Chemical Physics

205

114

View full text Add to dashboard Cite

We have used IR excitation to selectively create populations in admixtures of the zeroth-order states comprising the ∼3000 cm−1 ‘‘C–H stretching Fermi triad’’ of benzene. UV spectra of the 260 nm Ã(1B2u)←X̃(1A1g) transition in the IR-excited molecules show several new bands, which we have assigned. Final states in the UV transitions are some vibrational levels which have not been detected before, allowing us to find several excited-state vibrational frequencies. We have determined ν′3 =1327±3 cm−1, ν19 =1405±3 cm−1, and ν′20 =3084±5 cm−1. Also, vibrational structure which was unresolved in IR spectra of the ‘‘Fermi triad’’ was resolved in the UV double resonance spectra, confirming that the C–H stretching admixture is really a tetrad. The 3048, 3079, and 3101 cm−1 states had formerly been given the labels ν″20, ν″8+ν″19, and ν″1+ν″6+ν″19, respectively. Actually, the middle level most nearly resembles ν″1+ν″6+ν″19, and the 3101 cm−1 level is strongly mixed with ν″3+ν″6+ν″15. As predicted by molecular orbital theory, excited-state C–H bending and stretching frequencies are not very different from those in the ground state. Furthermore, we suggest that the four C–H stretching frequencies increase uniformly by ∼20 cm−1 in the excited state; reexamination of the Atkinson and Parmenter 260 nm Ã←X̃ spectrum leads us to reassign ν2 from 3130 to ∼3093 cm−1, which is 19 cm−1 above ν″2. There is a Fermi resonance between the ν6+ν′20 level and another level ∼13 cm−1 lower in energy; the strength of the perturbation is ∼18 cm−1. Possibilities for the perturbing vibrational state are ν6+ν′8+ν14 and ν′6+ν13.

show abstract

FTIR spectrum of benzene in a supersonic expansion

Cited by 44 publications

References 19 publications

Structure, Coordination, and Solvation of V⁺(benzene)_n Complexes via Gas Phase Infrared Spectroscopy

Structure, Coordination, and Solvation of V⁺(benzene)_n Complexes via Gas Phase Infrared Spectroscopy

Theoretical Study of Nascent Solvation in Ni⁺(Benzene)_m, m = 3 and 4, Clusters

Infrared–ultraviolet double resonance studies of benzene molecules in a supersonic beam

Contact Info

Product

Resources

About

FTIR spectrum of benzene in a supersonic expansion

Cited by 44 publications

References 19 publications

Structure, Coordination, and Solvation of V+(benzene)n Complexes via Gas Phase Infrared Spectroscopy

Structure, Coordination, and Solvation of V+(benzene)n Complexes via Gas Phase Infrared Spectroscopy

Theoretical Study of Nascent Solvation in Ni+(Benzene)m, m = 3 and 4, Clusters

Infrared–ultraviolet double resonance studies of benzene molecules in a supersonic beam

Contact Info

Product

Resources

About

Structure, Coordination, and Solvation of V⁺(benzene)_n Complexes via Gas Phase Infrared Spectroscopy

Structure, Coordination, and Solvation of V⁺(benzene)_n Complexes via Gas Phase Infrared Spectroscopy

Theoretical Study of Nascent Solvation in Ni⁺(Benzene)_m, m = 3 and 4, Clusters