A forgotten channel in the excited state dynamics of phenol–(ammonia)n clusters: hydrogen transfer

Pino, Gustavo A.; Grégoire, Gilles; Dedonder‐Lardeux, C.; Jouvet, Christophe; Martrenchard, S.; Solgadi, D.

doi:10.1039/a908497e

Cited by 108 publications

(134 citation statements)

References 53 publications

(15 reference statements)

Supporting

Mentioning

128

Contrasting

Order By: Relevance

“…5). It should be noted that the energy levels of the T 1 states of the phenol moieties are too low to induce the ionization or cleavage reactions [25]. The phenoxyl radical production through the ionization from the alkyl phenyl ether cation radicals may be negligible, because the C-O bond cleavage hardly occurs [26].…”

Section: Discussionmentioning

confidence: 99%

Photoinduced phenoxyl radical formation from ligno-p-cresol as studied by steady-state and time-resolved EPR spectroscopy

Tero‐Kubota

Tachikawa

Ito

et al. 2003

Chemical Physics Letters

View full text Add to dashboard Cite

Section: Discussionmentioning

confidence: 99%

Photoinduced phenoxyl radical formation from ligno-p-cresol as studied by steady-state and time-resolved EPR spectroscopy

Tero‐Kubota

Tachikawa

Ito

et al. 2003

Chemical Physics Letters

View full text Add to dashboard Cite

“…Numerous studies have been performed along this line, to characterize the proton transfer reactions in neutral and ionic clusters. ESPT has been thought to be observed in two model systems: 1-naphthol±ammonia (Cheshnovsky and Leutwyler 1985, Kim et al 1991, Knochenmuss et al 1993, Knochenmuss and Smith 1994, Yi and Scheiner 1996, Kelley and Bernstein 1999, Knochenmuss 1999a,b, Knochenmuss et al 1999, DedonderLardeux et al 2001, Knochenmuss et al 2001, and phenol±ammonia , Steadman and Syage 1990, Syage and Steadman 1991, Steadman and Syage 1992, Hineman et al 1993, Syage 1993a,b, Martrenchard-Barr a et al 1999, Pino et al 1999, Kim et al 2000, Pino et al 2000.…”

Section: The Excited State Proton Transfer Reaction: a Brief Historymentioning

confidence: 98%

“…Following the ESPT model, no protonated ammonia clusters should be detected. In fact they are (see ®gure 2), implying that there is no high barrier in the ionic potential (Pino et al 1999(Pino et al , 2000.…”

Section: The Key Experiments 321 Nanosecond Pump±probe Experimentsmentioning

confidence: 99%

Is there an Excited State Proton Transfer in phenol (or 1 -naphthol)-ammonia clusters? Hydrogen Detachment and Transfer to Solvent: A key for non-radiative processes in clusters

David¹,

Dedonder‐Lardeux²,

Jouvet³

2002

International Reviews in Physical Chemistry

Self Cite

View full text Add to dashboard Cite

This contribution highlights recent advances in the understanding of excited state dynamics in aromatic enols. This review will be mainly focused on the experimental and theoretical work performed on two model systems, 1-naphthol± ammonia and phenol±ammonia, and most particularly on cluster studies. These systems have long been thought to be prototypes for the famous`solvent-induced excited state proton transfer reaction', but recent results contradict this mechanism. The dynamics of these systems, excited in the S1 (ºº*) state, is not governed by couplings with ion pair states, inducing intracluster proton transfer, but rather linked to a crossing with a higher excited singlet state of the º¼* Rydberg state character, dissociative along the OH coordinate, leading to a hydrogen transfer from the hydroxyl group to the ammonia cluster via a non-adiabatic process, a mechanism also referred to as`concerted electron and proton transfer'. The crossing of the higher 1 º¼* state with lower excited 1 ºº* and ground states seems to be a general property in aromatic enols and azines (indole derivatives) and can help to understand the non-radiative decays in amino acid molecules as well as in DNA bases.

show abstract

“…The ESHT reaction is contrary to the traditional view that this cluster system will undergo an excited state proton transfer (ESPT) reaction as the pKa of this weak acid is lowered in the electronically excited state. 3 However, the ESHT reaction has been computationally predicted and experimentally confirmed in many systems including phenol, [4][5][6][7] halogenated phenols, 8,9 methylphenol, 10 thiophenol, [11][12][13] pyrrole, 14 indole, 15 and 3-methyl-indole. 16 The ESHT reaction of phenol is driven by a πσ* state that is repulsive along the O-H bond.…”

Section: Introductionmentioning

confidence: 99%

Effects of Amino Substitution on the Excited State Hydrogen Transfer in Phenol: A TDDFT Study

2009

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

When isolated phenol or a small phenol-solvent cluster is excited to the S1 state of ππ* character, the hydrogen atom of the hydroxyl group dissociates via a πσ* state that is repulsive along the O-H bond. We computationally investigated the substitution effects of an amino group on the excited state hydrogen transfer reaction of phenol. The time-dependent density functional theory (TDDFT) with B3LYP functional was employed to calculate the potential energy profiles of the ππ* and the πσ* excited states along the O-H coordinate, together with the orbital shape at each point, as the position of the substituent was varied. It was found that the amino substitution has an effect of lowering the πσ* state and enhancing the excited state hydrogen transfer reaction.

show abstract

A forgotten channel in the excited state dynamics of phenol–(ammonia)n clusters: hydrogen transfer

Cited by 108 publications

References 53 publications

Photoinduced phenoxyl radical formation from ligno-p-cresol as studied by steady-state and time-resolved EPR spectroscopy

Photoinduced phenoxyl radical formation from ligno-p-cresol as studied by steady-state and time-resolved EPR spectroscopy

Is there an Excited State Proton Transfer in phenol (or 1 -naphthol)-ammonia clusters? Hydrogen Detachment and Transfer to Solvent: A key for non-radiative processes in clusters

Effects of Amino Substitution on the Excited State Hydrogen Transfer in Phenol: A TDDFT Study

Contact Info

Product

Resources

About