Decay of the fluorescence anisotropy from isolated stilbene molecules

Negus, Daniel K.; Green, D.S.; Hochstrasser, Robin M.

doi:10.1016/0009-2614(85)80273-6

Cited by 33 publications

(37 citation statements)

References 13 publications

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“…(For reviews, see refs and .) The decay of the anisotropy at short times has also been observed in isolated molecules (see, e.g., refs −13), and this behavior serves as a fundamental probe of inertial motion at finite temperature in a manner analogous to the role it has long played in studies of diffusive reorientation in liquids. Both classical and quantum mechanical theoretical treatments based on free rigid rotor motion (see, e.g., refs and ) have been very successful at describing the decay, and the recurrences. , …”

Section: Orientation Of Free Moleculesmentioning

confidence: 90%

Molecular Structure and Orientation: Concepts from Femtosecond Dynamics

Baskin

Zewail

2001

J. Phys. Chem. A

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In this article, we are concerned with the basic concepts of molecular orientation, its dynamics on the femtosecond and picosecond time scales, and the direct relationship of the foregoing to determination of molecular structures. Our aim is to present a unified picture for the dynamics in different phases: coherent inertial in isolated molecules, partially coherent in dense fluids, and reaching the diffusive limit in liquids. We compare theory and experiment for reactive and nonreactive systems, with examples of studies from this laboratory in molecular beams, dense fluids, liquids, proteins, and micelles. We discuss the high precision achieved in molecular structural determination for large isolated molecules. Important to molecular orientation in space is the time scale, and we present here the two limits: quantum-state orientation (long time or continuous wave experiment) and classical-like orientation achieved with femtosecond resolution.

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Section: Orientation Of Free Moleculesmentioning

confidence: 90%

Molecular Structure and Orientation: Concepts from Femtosecond Dynamics

Baskin

Zewail

2001

J. Phys. Chem. A

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“…A key post-Hartree−Fock study is due to Quenneville and Marti ́nez 99 who used state-averaged CASPT2//CASSCF(2,2) computations (plus CASSCF (14,12) optimization of conical intersection) to study the path from trans-to cis-stilbene in the excited state. Their important contribution was the description of a pyramidalized stationary point reached in S 1 upon twisting without symmetry constraints, and of the nearby S 0 /S 1 intersection which likely is involved in the photoisomerization.…”

Section: ■ Introductionmentioning

confidence: 99%

“…A common present day standard for high-level calculations of excited states is multistate multireference (MS-MR) perturbation theory in its various implementations. The extended multiconfiguration quasi-degenerate second order perturbation theory XMCQDPT2 has been presented recently 132 as a correction for certain deficiencies of the previously known (14,14) active space encompasses the complete set of π-orbitals from 7π to 7π*, the reduced (10,10) space omits 7π, 6π, 6π*, and 7π*, and the minimum (2,2) space includes only the HOMO (1π) and the LUMO (1π*). MCQDPT2 approach.…”

Section: ■ Introductionmentioning

confidence: 99%

Photoisomerization of Stilbene: The Detailed XMCQDPT2 Treatment

Ioffe

Granovsky

2013

J. Chem. Theory Comput.

149

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We report the detailed XMCQDPT2/cc-pVTZ study of trans-cis photoisomerization in one of the core systems of both experimental and computational photochemistry-the stilbene molecule. For the first time, the potential energy surface (PES) of the S1 state has been directly optimized and scanned using a multistate multiconfiguration second-order perturbation theory. We characterize the trans-stilbene, pyramidalized (phantom), and DHP-cis-stilbene geometric domains of the S1 state and describe their stationary points including the transition states between them, as well as S1/S0 intersections. Also reported are the minima and the activation barriers in the ground state. Our calculations correctly predict the kinetic isotope effect due to H/D exchange at ethylenic hydrogens, the dynamic behavior of excited cis-stilbene, and trans-cis branching ratio after relaxation to S0 through a rather unsymmetric conical intersection. In general, the XMCQDPT2 results confirm the qualitative adequacy of the TDDFT (especially SF-TDDFT) picture of the excited stilbene but also reveal quantitative discrepancies that deserve further exploration.

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“…One expects that even more information on dynamics might be available by adding an extra dimension to such experiments and making polarization measurements as a function of time. In fact, our group12 and Negus et al 13 have reported polarization-dependent transients in isolated trans-stilbene which may reflect IVRET. 14 At this juncture, however, the lack of theoretical results on what and how certain processes are reflected in time-and polarization-dependent observables inhibits interpretation of these results.…”

Section: Introductionmentioning

confidence: 65%

“…The manifestations of purely rotational coherence in such experiments can differ in significant ways from the fluorescence case (especially if the probe ionization step proceeds through a resonant intermediate). The experiments of Negus et al 13 were done on Zrozzj-stilbene at high temperature (398 K) with detection of total (wavelength unresolved) fluorescence. Therefore, the effect of vibrational hot bands and the fact that different fluorescence bands may be characterized by different emission dipole directions must be considered.…”

Section: Resultsmentioning

confidence: 99%

Rephasing of collisionless molecular rotational coherence in large molecules

Felker¹,

Baskin²,

Zewail³

1986

J. Phys. Chem.

134

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We present experimental results on the rephasing of collisionless rotational coherence in jet-cooled trans-stilbene. The results represent the first observation of quantum coherence effects arising from the rotational level structure of molecules. We discuss the nature of the effect, its possible influence in time-resolved polarization experiments designed to probe intramolecular energy flow, and its possible uses as a new spectroscopic tool.

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Decay of the fluorescence anisotropy from isolated stilbene molecules

Cited by 33 publications

References 13 publications

Molecular Structure and Orientation: Concepts from Femtosecond Dynamics

Molecular Structure and Orientation: Concepts from Femtosecond Dynamics

Photoisomerization of Stilbene: The Detailed XMCQDPT2 Treatment

Rephasing of collisionless molecular rotational coherence in large molecules

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