Polarisabilités optiques moléculaires de dérivés benzèniques en solution déterminées par des mesures d'effet Kerr statique

Proutière, A.; Camail, M.

doi:10.1080/00268977500101291

Cited by 22 publications

(12 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…General formulae for multipole moments induced on the monomers in a molecular dimer by the field of the multipole moments of the other monomer are given in ref. 37, eqn (35), (36), and (40). These formulae contain the spherical components of the monomer multipole moments and polarizabilities.…”

Section: B Intensities Dipole Functionsmentioning

confidence: 99%

“…For the quadrupole moment and the polarizability of benzene we used the experimental values Q 2,0 = À6.46ea 0 2 , 38 a J = 81a 0 3 , and a > = 44a 0 3 . 39,40 The total long range dipole moment is the sum of the contributions in eqn (5) and (6). Both…”

Section: B Intensities Dipole Functionsmentioning

confidence: 99%

“…, 38 a J = 81a 0 3 , and a > = 44a 0 3 . 39,40 The total long range dipole moment is the sum of the contributions in eqn ( 5) and ( 6). Both d LR z and d LR x depend on the cap tilt angle b A , but not on the stem rotation angle g B , since both the quadrupole moment and the dipole polarizability of the benzene molecule have axial symmetry.…”

Section: B Intensities Dipole Functionsmentioning

confidence: 99%

See 2 more Smart Citations

Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study

Schnell

Erlekam

Bunker

et al. 2013

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We report a combined theoretical and microwave spectroscopy study of the internal dynamics of the benzene dimer, a benchmark system for dispersion forces. Although the extensive ab initio calculations and experimental work on the equilibrium geometry of this dimer have converged to a tilted T-shaped structure, the rich internal dynamics due to low barriers for internal rotation have remained largely unexplored. We present new microwave spectroscopy data for both the normal (C6H6)2 and partially deuterated (C6D6)(C6H6) dimers. The splitting patterns obtained for both species are unraveled and understood using a reduced-dimensionality theoretical approach. The hindered sixfold rotation of the stem can explain the observed characteristic 1 : 2 : 1 tunneling splitting pattern, but only the concerted stem rotation and tilt tunneling motion, accompanied by overall rotation of the dimer, yield the correct magnitude of the splittings and their strong dependence on the dimer angular momentum J that is essential to explain the experimental data. Also the surprising observation that the splittings are reduced by 30% for the mixed (C6D6)(C)(C6H6)(S) dimer in which only the cap (C) in the T-shaped structure is deuterated, while the rotating stem (S) monomer is the same as in the homodimer, is understood using this approach. Stark shift measurements allowed us to determine the dipole moment of the benzene dimer, μ = 0.58 ± 0.051 D. The assumption that this dipole moment is the vector sum of the dipole moments induced in the monomers by the electric field of the quadrupole on the other monomer yields a calculated value of μ = 0.63 D. Furthermore, the observed Stark behavior is typical for a symmetric top, another confirmation of our analysis.

show abstract

Section: B Intensities Dipole Functionsmentioning

confidence: 99%

Section: B Intensities Dipole Functionsmentioning

confidence: 99%

Section: B Intensities Dipole Functionsmentioning

confidence: 99%

See 1 more Smart Citation

Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study

Schnell

Erlekam

Bunker

et al. 2013

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…at the aug-cc-pV7Z level, in reasonable agreement with experiment ͑70.05 a.u. by Proutiére and Camail, 21 67.48 a.u. by Alms et al, 22 and 68.7 a.u.…”

Section: Polarizabilitymentioning

confidence: 99%

Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using Cholesky decompositions

Pedersen

Merás

Koch

2004

The Journal of Chemical Physics

115

100

View full text Add to dashboard Cite

A new implementation of the approximate coupled cluster singles and doubles CC2 linear response model using Cholesky decomposition of the two-electron integrals is presented. Significantly reducing storage demands and computational effort without sacrificing accuracy compared to the conventional model, the algorithm is well suited for large-scale applications. Extensive basis set convergence studies are presented for the static and frequency-dependent electric dipole polarizability of benzene and C 60 , and for the optical rotation of CNOFH 2 and (Ϫ)-trans-cyclooctene ͑TCO͒. The origin-dependence of the optical rotation is calculated and shown to persist for CC2 even at basis set convergence.

show abstract

“…Related to the hyperpolarizability tensor, the term can be neglected for compounds having y2 > 5 Á. 6 This correlation being established, the principal optical polarizabilities (an, a22, a33) of polar molecules may be calculated, in the optical valence hypothesis, from the three self-reliant equations 9M 2 -1 4 2 + 2 an + a22 + a33 = 3a…”

Section: Introductionmentioning

confidence: 99%

Intramolecular interactions. XXIV. Conformations of benzylic compounds. Molecular optical anisotropies, dipole moments, and Kerr constants

Camail¹,

Proutière²,

Verlaque³

1975

J. Phys. Chem.

View full text Add to dashboard Cite

For the series C6H5-CH2Z (Z = Me, Cl, Br, or CN), p-BrC6H4-CH2Br, and m-ClC6H4-CH2Z (Z = Cl or Br), from bond parameters, the molecular optical polarizabilities are calculated as a function of the rotational angle . They are used for relating 2, µ.2, and Sk to cos2 ( ). For the hypothesis of "locked" conformations, the experimental values are in agreement with a Ci symmetry. Comparison of the dihedral angles shows clear relationships with the steric hindrance of the Z substituents and with the electron withdrawing abilities of the p-Br and m-Cl substituents.

show abstract

Polarisabilités optiques moléculaires de dérivés benzèniques en solution déterminées par des mesures d'effet Kerr statique

Cited by 22 publications

References 5 publications

Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study

Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study

Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using Cholesky decompositions

Intramolecular interactions. XXIV. Conformations of benzylic compounds. Molecular optical anisotropies, dipole moments, and Kerr constants

Contact Info

Product

Resources

About