Rotationally resolved electronic spectroscopy of some divinylbenzenes in the gas phase. Platt’s rule revisited

Nguyen, Tri Van; Ribblett, Jason W.; Pratt, David W.

doi:10.1016/s0301-0104(02)00641-9

Cited by 11 publications

(22 citation statements)

References 16 publications

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“…We therefore tentatively assign the S 0 −S 1 transition as 1 A 1 − 1 B 2 , with the transition moment pointing perpendicular to the C 2 axis (Table ). This assignment is consistent with that deduced from the fully rotationally resolved spectra for the meta -divinylbenzenes by Nguyen et al…”

Section: Results and Analysissupporting

confidence: 92%

“…We therefore tentatively assign the S 0 -S 1 transition as 1 A 1 -1 B 2 , with the transition moment pointing perpendicular to the C 2 axis (Table 1). This assignment is consistent with that deduced from the fully rotationally resolved spectra for the meta-divinylbenzenes by Nguyen et al 21 Much of the structure in the mDEB R2PI spectrum can be assigned using the same vibrational modes found in the corresponding pDEB and phenylacetylene 18 spectra. The largest peak in the mDEB spectrum (465 cm -1 ) is assigned to 40 1 0 , where ν 40 is the same CsCtC bend as ν 20 in pDEB.…”

Section: Results and Analysissupporting

confidence: 89%

“…The CIS calculations do correctly predict the large difference, a factor of nearly 60, in the oscillator strengths of the first two excited states. This reordering of states has been previously discussed for phenylacetylene and several isomers of divinylbenzene …”

Section: Results and Analysissupporting

confidence: 66%

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Infrared and Ultraviolet Spectroscopy of Jet-Cooled ortho-, meta-, and para-Diethynylbenzene

Stearns

Zwier

2003

J. Phys. Chem. A

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The vibronic spectroscopy of ortho-, meta-, and para-diethynylbenzene (oDEB, mDEB, and pDEB) was studied by two-color resonant two photon ionization (R2PI). The symmetry allowed S 0 -S 1 origins of oDEB, mDEB, and pDEB were located at 33 515, 33 806, and 34 255 cm -1 , respectively, with the vibronic structure extending about 2000 cm -1 above the origin in oDEB and mDEB, but more than 3000 cm -1 in pDEB. Major peaks in each spectrum were attributed to vibronically induced bands, indicating strong coupling of the S 1 state to the S 2 state. Ground-state infrared spectra in the C-H stretch region (3000-3360 cm -1 ) were obtained using resonant ion-dip infrared spectroscopy (RIDIRS). In all three isomers, the acetylenic C-H stretch fundamental was split by Fermi resonance with a combination band composed of the CtC stretch and two quanta of the CtCsH bend. This Fermi resonance was detuned in the overtone region of pDEB, which showed a single peak at 6556 cm -1 . Infrared spectra were also recorded in the excited electronic state using a UV-IR-UV version of RIDIR spectroscopy. In all three isomers, the acetylenic C-H stretch fundamental was unshifted from the ground state, but no Fermi resonance was seen. In addition to the sharp C-H stretch features, the oDEB S 1 infrared spectrum showed a broad absorption stretching from 3050 to 3250 cm -1 . Selective deuteration of oDEB at the acetylenic hydrogens led to infrared spectra that showed the broad absorption despite the absence of the acetylenic C-H stretch, indicating that the IR absorption is electronic in nature. Characteristics of this second excited state and its potential relevance as a gateway to a photochemical Bergman cyclization are discussed. † Part of the special issue "Charles S. Parmenter Festschrift".

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Section: Results and Analysissupporting

confidence: 92%

Section: Results and Analysissupporting

confidence: 89%

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Infrared and Ultraviolet Spectroscopy of Jet-Cooled ortho-, meta-, and para-Diethynylbenzene

Stearns

Zwier

2003

J. Phys. Chem. A

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“…Pratt and co-workers have shown that unsymmetrical off-axis substitution in divinylbenzenes leads to a mixing of the L a and L b states. 50 The other limiting case is found, e.g., for 4-aminobenzonitrile. 1 In this case, we have a substitution symmetric with respect to the a-axis.…”

Section: Cc2/cc-pvtzmentioning

confidence: 89%

Determination of ground and excited state dipole moments via electronic Stark spectroscopy: 5-methoxyindole

Wilke

Meerts

et al. 2016

The Journal of Chemical Physics

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The dipole moments of the ground and lowest electronically excited singlet state of 5-methoxyindole have been determined by means of optical Stark spectroscopy in a molecular beam. The resulting spectra arise from a superposition of different field configurations, one with the static electric field almost parallel to the polarization of the exciting laser radiation, the other nearly perpendicular. Each field configuration leads to different intensities in the rovibronic spectrum. With an automated evolutionary algorithm approach, the spectra can be fit and the ratio of both field configurations can be determined. A simultaneous fit of two spectra with both field configurations improved the precision of the dipole moment determination by a factor of two. We find a reduction of the absolute dipole moment from 1.59(3) D to 1.14(6) D upon electronic excitation to the lowest electronically excited singlet state. At the same time, the dipole moment orientation rotates by 54(∘) showing the importance of the determination of the dipole moment components. The dipole moment in the electronic ground state can approximately be obtained from a vector addition of the indole and the methoxy group dipole moments. However, in the electronically excited state, vector addition completely fails to describe the observed dipole moment. Several reasons for this behavior are discussed.

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“…An important diagnostic of such mixing is the orientation of the molecular electronic TM. 16 Beyond this, at least a CASSCF/MP2 calculation is required to account in detail for the degeneracy of the orbitals and their configuration interaction. 18 Still, "low-level" calculations such as CIS/6-31G* are capable of reproducing most of the major effects.…”

Section: Discussionmentioning

confidence: 99%

Charge Redistribution on Electronic Excitation. Dipole Moments of cis- and trans-3-Aminophenol in Their S₀ and S₁ Electronic States

et al. 2004

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Rotationally resolved electronic spectroscopy in the gas phase, in the absence and presence of an applied electric field, has been used to distinguish the two conformers of 3-aminophenol (3AP) on the basis of differences in their electric dipole moments. cis-3AP has micro = 2.3 D, and trans-3AP has micro = 0.7 D, in their ground electronic states. The two observed values are approximately equal to those expected on the basis of bond dipole additivity rules. However, these rules fail to predict the large change in both the magnitude and the orientation of micro when the two conformers of 3AP absorb light. cis-3AP has micro = 3.3 D, and trans-3AP has micro = 1.7 D, in their excited S(1) electronic states; the angles of orientation of micro with respect to the a inertial axis change by 13 degrees and 38 degrees, respectively. This effect is attributed to (1)L(b)/(1)L(a) state mixing in the S(1) state.

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Rotationally resolved electronic spectroscopy of some divinylbenzenes in the gas phase. Platt’s rule revisited

Cited by 11 publications

References 16 publications

Infrared and Ultraviolet Spectroscopy of Jet-Cooled ortho-, meta-, and para-Diethynylbenzene

Infrared and Ultraviolet Spectroscopy of Jet-Cooled ortho-, meta-, and para-Diethynylbenzene

Determination of ground and excited state dipole moments via electronic Stark spectroscopy: 5-methoxyindole

Charge Redistribution on Electronic Excitation. Dipole Moments of cis- and trans-3-Aminophenol in Their S₀ and S₁ Electronic States

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Rotationally resolved electronic spectroscopy of some divinylbenzenes in the gas phase. Platt’s rule revisited

Cited by 11 publications

References 16 publications

Infrared and Ultraviolet Spectroscopy of Jet-Cooled ortho-, meta-, and para-Diethynylbenzene

Infrared and Ultraviolet Spectroscopy of Jet-Cooled ortho-, meta-, and para-Diethynylbenzene

Determination of ground and excited state dipole moments via electronic Stark spectroscopy: 5-methoxyindole

Charge Redistribution on Electronic Excitation. Dipole Moments of cis- and trans-3-Aminophenol in Their S0 and S1 Electronic States

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Product

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Charge Redistribution on Electronic Excitation. Dipole Moments of cis- and trans-3-Aminophenol in Their S₀ and S₁ Electronic States