Jet spectroscopy of perylene complexes: Comparisons of TMS, carbon dioxide, ethylene and butadiene

Babbitt, R. Jefferson; Doxtader, Mark M.; Bhattacharya, Ashish K.; Topp, Michael R.

doi:10.1016/0301-0104(87)80006-x

Cited by 11 publications

(6 citation statements)

References 45 publications

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“…However, S 1 excited-state stabilization can also arise from an increase of the dispersive interactions and from the change of quadrupole-induced-dipole interactions. Van der Waals-type small electronic red-shifts δν have been studied by Topp and co-workers for complexes of perylene with the nonpolar molecules CO 2 , ethene, and butadiene, all of which are poor electron acceptors . They observed a spectral red-shift of δν = −162 cm –1 for perylene·ethene .…”

Section: Introductionmentioning

confidence: 99%

“…Perylene is a planar aromatic that offers a large surface, see Figure , for the interaction with electron acceptor molecules such as planar ethene derivatives. Its relatively low ionization potential of 6.96 eV makes perylene a good electron donor, and its vibronic spectra have been studied and convincingly assigned. − A number of jet-cooled perylene·R n van der Waals complexes, with R = Ne, Ar, Kr, and Xe and n = 1–4, and perylene·X molecular complexes, with X = ethene, butadiene, CO 2 , and tetramethylsilane, − have been spectroscopically investigated. Intermolecular interactions in perylene complexes have so far only been investigated by empirical force-field methods …”

Section: Introductionmentioning

confidence: 99%

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Structure and Intermolecular Vibrations of Perylene·trans-1,2-Dichloroethene, a Weak Charge-Transfer Complex

et al. 2013

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The vibronic spectra of strong charge-transfer complexes are often congested or diffuse and therefore difficult to analyze. We present the spectra of the π-stacked complex perylene trans-1,2-dichloroethene, which is in the limit of weak charge transfer, the electronic excitation remaining largely confined to the perylene moiety. The complex is formed in a supersonic jet, and its S0 ↔ S1 spectra are investigated by two-color resonant two-photon ionization (2C-R2PI) and fluorescence spectroscopies. Under optimized conditions, vibrationally cold (T(vib) ≈ 9 K) and well resolved spectra are obtained. These are dominated by vibrational progressions in the “hindered-rotation” Rc intermolecular vibration with very low frequencies of 11 (S0) and 13 cm(–1) (S1). The intermolecular Tz stretch and the Ra and Rb bend vibrations are also observed. The normally symmetry-forbidden intramolecular 1a(u) “twisting” vibration of perylene also appears, showing that the π- stacking interaction deforms the perylene moiety, lowering its local symmetry from D2h to D2. We calculate the structure and vibrations of this complex using six different density functional theory (DFT) methods (CAM-B3LYP, BH&HLYP, B97-D3, ωB97X-D, M06, and M06-2X) and compare the results to those calculated by correlated wave function methods (SCS-MP2 and SCS-CC2). The structures and vibrational frequencies predicted with the CAM-B3LYP and BH&HLYP methods disagree with the other calculations and with experiment. The other four DFT and the ab initio methods all predict a π-stacked “centered” structure with nearly coplanar perylene and dichloroethene moieties and intermolecular binding energies of D(e) = −20.8 to −26.1 kJ/mol. The 000 band of the S0 → S1 transition is red-shifted by δν = −301 cm(–1) relative to that of perylene, implying that the D(e) increases by 3.6 kJ/mol or 15% upon electronic excitation. The intermolecular vibrational frequencies are assigned to the calculated Rc, Tz, Ra, and Rb vibrations by comparing to the observed/calculated frequencies and S0 ↔ S1 Franck–Condon factors. Of the three TD-DFT methods tested, the hybrid-meta-GGA functional M06-2X shows the best agreement with the experimental electronic transition energies, spectral shifts, and vibronic spectra, closely followed by the ωB97X-D functional, while the M06 functional gives inferior results.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structure and Intermolecular Vibrations of Perylene·trans-1,2-Dichloroethene, a Weak Charge-Transfer Complex

et al. 2013

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“…The extensive progressions are consistent with a geometry change between and SI in which the C02 molecule is displaced parallel to the aromatic plane. 35 The more usual approaches to measure binding energies, such as picosecond timedomain fluorescence spectroscopy, are limited by the strong overlap of the emission spectra from (a) excited complexes, (b) nascent bare molecules, and (c) background bare molecules absorbing in the same region as thevibronic bands of the complex. The upper trace in Figure 14 shows part of the hole-burning spectrum of ~e r y l e n e / C O~~~ in the energy regime 1025-1450 cm-1, relative to the 0 ; transition of bare perylene.…”

Section: Peryleneln2mentioning

confidence: 99%

Hot-band spectroscopy of ground-state levels of perylene following predissociation of van der Waals complexes

Wittmeyer¹,

Topp²

1993

J. Phys. Chem.

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Experiments involving laser-induced hot bands have interrogated the energies and populations of ground-state vibrational levels of perylene. In the bare molecule, many ground-state levels persist into the 10-7-106-s regime without significant relaxation. Even in the perylene/Arl van der Waals complex, a ground-state quantum of 353 cm-l persists for >120 ns. On the other hand, residual collisions in the expanding free jet cause significant relaxation of energy deposited in low-energy (G) modes of perylene. Hot bands of free perylene are also generated following vibrational predissociation of van der Waals complexes. The argon, methane, and nitrogen complexes all show efficient hot-band population and show distribution of energy into low-energy, out-of-plane modes of the product aromatic molecule at higher energies. The COz complex dissociated at 11270 cm-1 in SI and the ethylene complex at 11320 cm-l. Corresponding ground-state binding energies are S1235 and 1 1 160 cm-l. In these two cases, hot-band excitation spectroscopy at x2-cm-l resolution provided the means to detect the onset of hot bands of nascent free perylene, as the pump laser scanned through a congested region of the spectrum.

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“…The concept of intermolecular charge-transfer (CT) electronic transitions was introduced by Mulliken in 1952 and has remained a widely studied subject. − Perylene-based CT complexes are well-suited for investigating CT excitations because it is a planar aromatic with a large adsorption area for planar acceptor molecules and a low adiabatic ionization potential AIP = 6.96 eV, which makes it a good π-electron donor. , Finally, perylene has a well-characterized vibronic spectrum. − These properties allow one to investigate a range of different acceptor molecules on the CT transitions. We previously reported the vibronic spectra of the mild CT complex perylene· trans -1,2-dichloroethene …”

Section: Introductionmentioning

confidence: 99%

“…Topp and coworkers have shown that perylene complexes with one and with two solvent (S) molecules that are van-der-Waals dispersively bonded to opposite sides (the so-called trans 1:2 complexes) exhibit spectral redshifts that are closely additive. Thus, the ratio of the redshift of the 1:2 relative to the 1:1 perylene·S complexes are between 1.85 to 1.95 for tetramethylsilane, 12 butadiene, 12 1-chlorobutane, 13 benzene 13 and 1-chloropentane. 13 In contrast a cis-isomer was observed for perylene·(ethene) 2 with both ethene units adsorbing on the same side of perylene.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene)_n, n = 1,2

2015

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The S 0 ↔ S 1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene) 2 , P·(4ClE) 2 , are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets.The S 0 → S 1 vibrationless transitions of P·4ClE and P·(4ClE) 2 are shifted by δν = −451 and −858 cm −1 relative to perylene, translating to excited state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The redshift is ∼ 30% larger than that of perylene·trans-1,2-dichloroethene, so the increase in chlorination increases the excited-state stabilization and charge-transfer character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1a u ) vibration (42 cm −1 in S 0 and 55 cm −1 in S 1 ), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (T z ) and internal-rotation (R c ) vibrations are weak, so * To whom correspondence should be addressed

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Jet spectroscopy of perylene complexes: Comparisons of TMS, carbon dioxide, ethylene and butadiene

Cited by 11 publications

References 45 publications

Structure and Intermolecular Vibrations of Perylene·trans-1,2-Dichloroethene, a Weak Charge-Transfer Complex

Structure and Intermolecular Vibrations of Perylene·trans-1,2-Dichloroethene, a Weak Charge-Transfer Complex

Hot-band spectroscopy of ground-state levels of perylene following predissociation of van der Waals complexes

Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene)_n, n = 1,2

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Jet spectroscopy of perylene complexes: Comparisons of TMS, carbon dioxide, ethylene and butadiene

Cited by 11 publications

References 45 publications

Structure and Intermolecular Vibrations of Perylene·trans-1,2-Dichloroethene, a Weak Charge-Transfer Complex

Structure and Intermolecular Vibrations of Perylene·trans-1,2-Dichloroethene, a Weak Charge-Transfer Complex

Hot-band spectroscopy of ground-state levels of perylene following predissociation of van der Waals complexes

Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene)n, n = 1,2

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Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene)_n, n = 1,2