The application of a recently developed theoretical method, CS–INDO/CI, to the study of the sections of the potential-energy surfaces of the ground and four lowest excited singlet states of 1,1′-binaphthyl corresponding to the coordinate of twisting around the inter-ring 1,1′-bond has proved to be successful in explaining the measured spectroscopic and photophysical properties of this molecule. All the changes observed in its spectroscopy and photophysics on going from low-temperature rigid solutions to room-temperature fluid solutions (strong bathochromic shift of the fluorescence maximum, change in the Snâ†�S1 absorption spectrum, shortening of the fluorescence lifetime by an order of magnitude) are qualitatively accounted for in terms of the calculated potential-energy curves. In particular, the S1 state experiences a drastic change in its electronic nature (from Lb to La) when the interplanar angle is allowed to relax from the near-orthogonal ground-state conformation to the trans twisted S1 equilibrium conformation (ϕ≈ 130 °). A comparison with the results of previous theoretical approaches stresses the reliability of the CS–INDO/CI method and the wealth of information on potential-energy surfaces which can be achieved through its application.

Potential-energy curves of the torsional mode of 1,1′-binaphthyl in the ground and lowest excited singlet states. A CS–INDO/CI study / Baraldi, Ivan; Ponterini, Glauco; Momicchioli, Fabio. - In: JOURNAL OF THE CHEMICAL SOCIETY. FARADAY TRANSACTIONS II. - ISSN 0300-9238. - ELETTRONICO. - 83:(1987), pp. 2139-2149. [10.1039/F29878302139]

Potential-energy curves of the torsional mode of 1,1′-binaphthyl in the ground and lowest excited singlet states. A CS–INDO/CI study

BARALDI, Ivan;PONTERINI, Glauco;MOMICCHIOLI, Fabio
1987

Abstract

The application of a recently developed theoretical method, CS–INDO/CI, to the study of the sections of the potential-energy surfaces of the ground and four lowest excited singlet states of 1,1′-binaphthyl corresponding to the coordinate of twisting around the inter-ring 1,1′-bond has proved to be successful in explaining the measured spectroscopic and photophysical properties of this molecule. All the changes observed in its spectroscopy and photophysics on going from low-temperature rigid solutions to room-temperature fluid solutions (strong bathochromic shift of the fluorescence maximum, change in the Snâ†�S1 absorption spectrum, shortening of the fluorescence lifetime by an order of magnitude) are qualitatively accounted for in terms of the calculated potential-energy curves. In particular, the S1 state experiences a drastic change in its electronic nature (from Lb to La) when the interplanar angle is allowed to relax from the near-orthogonal ground-state conformation to the trans twisted S1 equilibrium conformation (ϕ≈ 130 °). A comparison with the results of previous theoretical approaches stresses the reliability of the CS–INDO/CI method and the wealth of information on potential-energy surfaces which can be achieved through its application.
83
2139
2149
Potential-energy curves of the torsional mode of 1,1′-binaphthyl in the ground and lowest excited singlet states. A CS–INDO/CI study / Baraldi, Ivan; Ponterini, Glauco; Momicchioli, Fabio. - In: JOURNAL OF THE CHEMICAL SOCIETY. FARADAY TRANSACTIONS II. - ISSN 0300-9238. - ELETTRONICO. - 83:(1987), pp. 2139-2149. [10.1039/F29878302139]
Baraldi, Ivan; Ponterini, Glauco; Momicchioli, Fabio
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11380/747217
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