Theoretical Study of the Internal Charge Transfer in Aminobenzonitriles

Serrano‐Andrés, Luis; Merchán, Manuela; Roos, Bjoern O.; Lindh, Roland

doi:10.1021/ja00116a024

Cited by 199 publications

(271 citation statements)

References 8 publications

Supporting

Mentioning

230

Contrasting

Order By: Relevance

“…Electronic structure methods used to examine the details of the emission process have included linear-response time-dependent density functional theory [12][13][14] (LR-TDDFT), single-reference wavefunction methods such as TDHF/CIS, 15 DFT/SCI, 16 CC2, 17 and ADC(2), 18 and multi-reference wavefunction methods such as CASSCF [19][20][21] and CASPT2. [22][23][24][25] Even though a large number of experimental and theoretical data have been generated on the emission properties of DMABN and its chemical derivatives, much less information is available on the early nonadiabatic, i.e., non-Born-Oppenheimer, relaxation pathway following DMABN photoexcitation. Most theoretical and experimental studies agree that, at least in the gas phase, DMABN is initially promoted to its second excited state, which has ICT character.…”

Section: Scheme 1 4-(nn-dimethylamino)-benzonitrile (Dmabn)mentioning

confidence: 99%

Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

2017

View full text Add to dashboard Cite

The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractThe ultrafast decay dynamics of 4-(N,N-dimethylamino)benzonitrile (DMABN) following photoexcitation was studied with the ab initio multiple spawning (AIMS) method, combined with GPU-accelerated linear-response time-dependent density functional theory (LR-TDDFT). We validate the LR-TDDFT method for this case and then present a detailed analysis of the first ≈200 fs of DMABN excited-state dynamics. Almost complete nonadiabatic population transfer from S 2 (the initially populated bright state) to S 1 takes place in less than 50 fs, without significant torsion of the dimethylamino (DMA) group.Significant torsion of the DMA group is only observed after the nuclear wavepacket reaches S 1 and acquires locally-excited electronic character. Our results show that torsion of the DMA group is not prerequisite for nonadiabatic transitions in DMABN, although such motion is indeed relevant on the lowest excited state (S 1 ).Curchod, et al. -DMABN -Page 2

show abstract

Section: Scheme 1 4-(nn-dimethylamino)-benzonitrile (Dmabn)mentioning

confidence: 99%

Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

2017

View full text Add to dashboard Cite

show abstract

“…However, this first work does not give detailed structural information. Posteriorly, Serrano et al, 24 Lommatzsch and Brutschy 38 and Kolek et al 19 optimized the molecule at the CASSCF, HF/6-31CCG ŁŁ and MP2/6-31G Ł levels of theory respectively. These geometries are in very good agreement with the values computed in the present study, although they are less accurate than our present data.…”

Section: Geometry Optimizationmentioning

confidence: 99%

4‐Aminobenzonitrile: ab initio calculations, FTIR and Raman spectra

Palafox

Rastogi

Vats

2006

J Raman Spectroscopy

View full text Add to dashboard Cite

The experimental IR (in different matrices) and Raman spectra of 4-aminobenzonitrile molecule were recorded. The results were compared with theoretical values. Geometry, vibrational wavenumbers and thermodynamic parameters were calculated using DFT quantum chemical methods. With the help of specific scaling procedures, the experimentally observed FTIR and Raman vibrational wavenumbers were analyzed and assigned to different normal modes of the molecule. The error obtained was, in general, very low. The contributions of the different modes to each wavenumber were determined using potential energy distributions (PEDs). Other general conclusions were also deduced.

show abstract

“…The TICT model of the stuctural change is also supported by all quantum chemical calculations, e.g. [8,9,30].…”

Section: The Nature Of the Highly Polar Statementioning

confidence: 58%

“…Roos et al [8] demonstrated that the pyramidalization of DMABN does not lead to any markedly polar structures. Very similar results are obtained by Gorse and Pesquer [30] for both, DMABN and the benzaldehyde derivative DMABA, including the solvation effects calculated for strongly polar solvents.…”

Section: Inversional Mode?mentioning

confidence: 99%

“…Quantum chemical calculations, starting from early papers [3] to the recent highly advanced quantum-chemical description of the DMABN molecule by Roos et al [8], support the existence of a highly polar state (μ 15-19 D) as one of the lowest excited states in the free molecule in its twisted (orthogonal) conformation; stabilization by polar solvents turns this state to the lowest excited singlet state (inaccessible directly in absorption, due to the Franck-Condon ule). Such result has been obtained also for p-dimethylaminobenzaldehyde (DMABA), a carbonyl derivative closely related to, and of the same π-electronic stucture as, DMAA and DOAA [9].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Picosecond Transient Absorption Spectra and the Twisted Intramolecular Charge Transfer Phenomenon

et al. 1995

View full text Add to dashboard Cite

An improved model of a ckputer-controlled picosecond absorption spectrometer was designed and constructed. Its operatioii is described, and applied to the measurement of transient spectra of p-N, N-dioctylamino--acetophenone. The spectroscopy and photophysics of this ckpound are ckpared to the other ckpounds exhibiting the dual fluorescence, assigned usually to the adiabatic formation of the "twisted" intramolecular charge transfer excited state. The data are discussed in relatioii to alternative suggestion of an inversioii of the pyramidal amino nitrogen atk. The whole evidence supports the decoupling of the π-electronic systems of D+ and A-in the D+-A -polar excited state, in full accord with the "twisted" intramolecular charge transfer model. The peculiar behaviour of the long alkyl -NR2 derivatives (favouring the "twisted" intramolecular charge transfer state emission) seems to be primarily due to the decreasing oxidation potential of such electron donor groups.

show abstract

Theoretical Study of the Internal Charge Transfer in Aminobenzonitriles

Cited by 199 publications

References 8 publications

Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

Ab Initio Multiple Spawning Photochemical Dynamics of DMABN Using GPUs

4‐Aminobenzonitrile: ab initio calculations, FTIR and Raman spectra

Picosecond Transient Absorption Spectra and the Twisted Intramolecular Charge Transfer Phenomenon

Contact Info

Product

Resources

About