Vibrational predissociation dynamics and internal rotation in aromatic van der Waals complexes

Gilbert, B.; Parmenter, C. S.; Su, M.‐C.; Oh, Hyuck Keun; Zhao, Z. Q.

doi:10.1007/bf01081062

Cited by 10 publications

(12 citation statements)

References 42 publications

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“…5,17 In contrast, we will show that the dissociation kinetics from various pumped levels in the Ne complex is often too slow to compete with fluorescence decay of the S 1 complex. For these cases, the cluster dissociation kinetics occurs on time scales similar to that of cluster fluorescence.…”

Section: Introductionmentioning

confidence: 80%

“…5,50 The ring modes of pFT are to a surprising extent little changed 55,56 from those of pDFB so that the boost in dissociation rates must be related to the methyl group internal rotation. It is p-fluorotoluene-Ar ͑pFT-Ar͒ in which the ring has been modified by the replacement of a fluorine with a CH 3 group.…”

Section: Modeling Of Dissociation In Pdfb Van Der Waals Complexesmentioning

confidence: 99%

“…The pDFB-Ar complex including the complex cation is particularly well studied, [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] but much is also known about the pDFB-N 2 5,16 -19 complex. The pDFB-Ar complex including the complex cation is particularly well studied, [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] but much is also known about the pDFB-N 2 5,16 -19 complex.…”

Section: Introductionmentioning

confidence: 99%

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Characteristics and relaxation dynamics of van der Waals complexes between p-difluorobenzene and Ne

Jayasekharan

Parmenter²

2004

The Journal of Chemical Physics

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Characteristics of the single and double Ne van der Waals complexes of p-difluorobenzene (pDFB) have been explored with ultraviolet fluorescence excitation and dispersed fluorescence spectroscopy. Eight S(1)-S(0) fluorescence excitation bands involving six ring modes of pDFB-Ne and two bands of pDFB-Ne(2) have been identified. Band assignments are confirmed by dispersed fluorescence from the pumped band. Shifts of the complex bands from the analogous monomer bands are generally 4 cm(-1) to the red for pDFB-Ne and 8 cm(-1) for pDFB-Ne(2). None of the observed ring modes is significantly perturbed by complexation in either the S(1) or S(0) states. The pDFB-Ne S(1) van der Waals binding energy D(0')

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Section: Introductionmentioning

confidence: 80%

Section: Modeling Of Dissociation In Pdfb Van Der Waals Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Characteristics and relaxation dynamics of van der Waals complexes between p-difluorobenzene and Ne

Jayasekharan

Parmenter²

2004

The Journal of Chemical Physics

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“…The convenience, in the near UV, of the S 0 -S 1 transitions in aromatic molecule-X complexes (X = rare-gas atom, small molecule), coupled with the large fluorescence quantum yield of the S 1 states, has long made these molecules particular favourites for IVR/VP studies. Dispersed, or single vibrational level, fluorescence spectroscopy has been applied to the study of VP in rare-gas clusters of benzene, [3] aniline, [4,5] s-tetrazine, [6,7] p-difluorobenzene (p-DFB), [8,9] p-fluorotoluene(p-FT) [8] and aminophenol [10]. For low-lying S 1 vibrational levels, the overall VP process has often been found to be mode-specific reflecting the considerable variation in IVR rate following excitation of different vibrational modes.…”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13] This is particularly dramatic in p-FT for which the FT final state distribution is essentially statistical with no sign of the highly modeselective distribution observed, e.g., in p-DFB. [8] It is believed that, during the motion associated with the methyl group rotation, repulsion between the methyl group and atoms of the ring results in ring puckering which significantly enhances the IVR rate. [11,13,14] Secondly, the effects of different cluster partners can be explored.…”

Section: Introductionmentioning

confidence: 99%

Vibrational predissociation in weakly-bound clusters: A dispersed fluorescence study of toluene rare-gas complexes

Campo

Mackenzie

2008

Chemical Physics Letters

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The vibrational predissociation (VP) dynamics of toluene-Ar and toluene-Ne complexes have been investigated using single vibronic level fluorescence spectroscopy. For several levels, comparison of the dispersed fluorescence spectra with those from monomer levels permits the identification of the final monomer vibrational level. Pumping of the low-lying S 1 1 0 1 0 1 0 25 24 13 / or 1 0 37 transitions in toluene-Ar, for example, gives rise to efficient VP leaving the resulting toluene monomer in its vibrationless S 1 state. By contrast, in the case of toluene-Ne, VP following 1 37 level pumping leaves the toluene molecule in an excited 1 16 level which is optically inaccessible from the ground state.

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Participation of Methyl Internal Rotation in the Vibrational Predissociation of the Aromatic van der Waals Complex p‐Fluorotoluene‐Ar

Zhao

Parmenter

1995

Ber Bunsenges Phys Chem

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S1‐S0 fluorescence excitation and dispersed fluorescence spectra from p‐fluorotoluene‐Ar (pFT‐Ar) formed in a supersonic expansion are used to characterize the vibrational predissociation (VP) from S1 complex levels with 800, 1200 and 2000 cm−1 of vibrational energy. VP from the lower level occurs in at least 12 vibrational channels that involve only the three lowest energy pFT ring modes. VP from the higher levels is different, but those two levels are a matched pair with respect to their VP characteristics. They have almost identical channels and branching ratios, including a dominant channel producing free pFT in its zero point level. That channel requires conversion of as much as 1800 cm−1 of ring mode vibrational energy into translational and rotational energy. These behaviors appear to be unique among the aromatic van der Waals complexes so far studied, particularly with respect to the non‐selective nature of the VP channels. Evidence pointing to the active participation of the methyl internal rotation in the VP dynamics is presented. Conjecture is offered about how this internal rotation contributes to the highly unusual VP characteristics.

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Vibrational predissociation dynamics and internal rotation in aromatic van der Waals complexes

Cited by 10 publications

References 42 publications

Characteristics and relaxation dynamics of van der Waals complexes between p-difluorobenzene and Ne

Characteristics and relaxation dynamics of van der Waals complexes between p-difluorobenzene and Ne

Vibrational predissociation in weakly-bound clusters: A dispersed fluorescence study of toluene rare-gas complexes

Participation of Methyl Internal Rotation in the Vibrational Predissociation of the Aromatic van der Waals Complex p‐Fluorotoluene‐Ar

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