Intracluster hydrogen transfer followed by dissociation in the phenol–(NH3)3 excited state: PhOH(S1)–(NH3)3→PhO•+(NH4)(NH3)2

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

doi:10.1063/1.480437

Cited by 86 publications

(52 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1][2][3] The recent paper of the group of M. Fujii, probing the NH 4 (NH 3 ) n-1 radical product coming from the reaction, has definitively assessed that, for small clusters, the PhOH*-(NH 3 ) n excited-state dynamics are governed by the H transfer mechanism. 4 In the 1-1 complex, the reaction is indirectly evidenced by measurement of the excited PhOH*-(NH 3 ) complex lifetime, which is abnormally short (1 ns or less as compared to lifetimes of the order of 10 ns for other phenol-solvent complexes [5][6][7][8][9] ).…”

Section: Introductionmentioning

confidence: 99%

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH₃)_n Molecular Clusters?

et al. 2001

Self Cite

View full text Add to dashboard Cite

A deuterium atom transfer mechanism has been studied in the excited state of perdeuterated phenol-(ND 3 ) n clusters and compared to the hydrogen atom transfer process evidenced in phenol-(NH 3 ) n)1,4 cluster excited state. A strong H/D effect is observed implying a tunneling reaction process. In view of these results, the question of the competition between proton transfer and H transfer is raised. An alternative to the excitedstate proton-transfer dynamics paradigm is proposed to explain the present and previous observations. Good agreement with experimental observations can be obtained with the following three propositions: excitedstate H atom transfer occurs for n ) 1 to 6; ground-state proton transfer takes place for n g 6 and direct excitation of ground-state proton transferred structures leads to fast evaporation/relaxation events in the excited state; excited-state proton transfer, although energetically favored for cluster sizes n g 4, is not observed, probably because its rate is slow compared to the H transfer reaction rate.

show abstract

Section: Introductionmentioning

confidence: 99%

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH₃)_n Molecular Clusters?

et al. 2001

Self Cite

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] Recently, phenol/ammonia clusters, PhOH-(NH 3 ) n , have attracted renewed attention since Jouvet and co-workers proposed that not proton transfer, but hydrogen transfer ͑ESHT͒, occurs in S 1 . [19][20][21][22] In Paper I, we reported on the electronic spectra of the reaction products. By comparing them with the electronic spectra of (NH 3 ) nϪ1 NH 4 generated by the photolysis of pure ammonia clusters, we proved that the reaction products are the (NH 3 ) nϪ1 NH 4 produced by the ESHT.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen transfer in photo-excited phenol/ammonia clusters by UV–IR–UV ion dip spectroscopy and ab initio molecular orbital calculations. II. Vibrational transitions

Ishiuchi

Daigoku

Saeki

et al. 2002

The Journal of Chemical Physics

View full text Add to dashboard Cite

Hydrogen transfer dynamics in a photoexcited phenol/ammonia (1:3) cluster studied by picosecond time-resolved UV-IR-UV ion dip spectroscopy High-level ab initio calculations for the four low-lying families of minima of ( H 2 O ) 20 . II. Spectroscopic signatures of the dodecahedron, fused cubes, face-sharing pentagonal prisms, and edge-sharing pentagonal prisms hydrogen bonding networks J. Chem. Phys. 122, 134304 (2005); 10.1063/1.1864892Picosecond IR-UV pump-probe spectroscopic study of the dynamics of the vibrational relaxation of jet-cooled phenol. II. Intracluster vibrational energy redistribution of the OH stretching vibration of hydrogen-bonded clusters Hydrogen transfer in photoexcited phenol/ammonia clusters by UV-IR-UV ion dip spectroscopy and ab initio molecular orbital calculations. I. Electronic transitionsThe vibrational spectra of phenol/ammonia clusters ͑1:2-5͒ in S 0 and those of their photochemical reaction products, (NH 3 ) nϪ1 NH 4 (nϭ2 -5), which are generated by excited-state hydrogen transfer, have been measured by UV-IR-UV ion dip spectroscopy. The geometries, IR spectra and normal modes of phenol-(NH 3 ) n (nϭ1 -5) have been examined by ab initio molecular orbital calculations, at the second-order Møller-Plesset perturbation theory level with large basis sets. For the nϭ2 and 3 reaction products, similar vibrational analyses have been carried out. From the geometrical information of reactants and products, it has been suggested that the reaction products have memories of the reactant's structure, which we call ''memory effect.''

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

Intracluster hydrogen transfer followed by dissociation in the phenol–(NH3)3 excited state: PhOH(S1)–(NH3)3→PhO•+(NH4)(NH3)2

Cited by 86 publications

References 19 publications

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH₃)_n Molecular Clusters?

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH₃)_n Molecular Clusters?

Hydrogen transfer in photo-excited phenol/ammonia clusters by UV–IR–UV ion dip spectroscopy and ab initio molecular orbital calculations. II. Vibrational transitions

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

Contact Info

Product

Resources

About

Intracluster hydrogen transfer followed by dissociation in the phenol–(NH3)3 excited state: PhOH(S1)–(NH3)3→PhO•+(NH4)(NH3)2

Cited by 86 publications

References 19 publications

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH3)n Molecular Clusters?

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH3)n Molecular Clusters?

Hydrogen transfer in photo-excited phenol/ammonia clusters by UV–IR–UV ion dip spectroscopy and ab initio molecular orbital calculations. II. Vibrational transitions

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

Contact Info

Product

Resources

About

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH₃)_n Molecular Clusters?

Has the Excited State Proton Transfer Ever Been Observed in Phenol−(NH₃)_n Molecular Clusters?