Excited state structure of 4-(dimethylamino)benzonitrile studied by femtosecond mid-infrared spectroscopy and ab initio calculations

Chudoba, C.; Kummrow, A.; Dreyer, J.; Stenger, Jens; Nibbering, Erik T. J.; Elsaesser, Thomas; Zachariasse, Klaas A.

doi:10.1016/s0009-2614(99)00711-3

Cited by 101 publications

(139 citation statements)

References 24 publications

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“…At 350 nm, which is slightly on the blue side of the LE emission maximum, the fluorescence time profiles decay exponentially to a value close to zero. The lifetime measured for DMABN at room temperature (3.7 ± 0.4 ps) is fully consistent with results of other fs studies (essentially 4.0 ps) reported in the literature [13,14]. The observation that the use of 290, 276 or 266 nm excitation did not result in different lifetime values for DMABN supports the view that vibrational cooling due to the excess energy present for our short wavelength excitation (267 nm) is not of importance for the kinetics measured in our study.…”

supporting

confidence: 91%

“…The present measurement is the first one to compare these values under 'standard conditions', i.e. in the polar solvent acetonitrile at room temperature, where most of the previous sub-ps measurements were done [13,14]. For both pairs of compounds, DMABN/DMABE and PYRBN/ PYRBN, the ratio of the rate constants amounts to about 4 in favour of the ester.…”

Section: Comparison Of Derivatives With Variation Of the Donor Group mentioning

confidence: 84%

“…Kinetic measurements with sub-ps time resolution have been possible recently, among them transient absorption [13], infrared [14,15], Raman [16] and mass spectral analysis [17]. Especially the kinetics in acetonitrile at room temperature are well characterized being situated around 4 ps [13,14].…”

Section: Introductionmentioning

confidence: 99%

“…Especially the kinetics in acetonitrile at room temperature are well characterized being situated around 4 ps [13,14]. The low temperature viscosity-dependent behaviour was not studied with this high time resolution.…”

Section: Introductionmentioning

confidence: 99%

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Entropic effects in excited state CT reactions

Pigliucci

Vauthey

Rettig

2009

Chemical Physics Letters

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a b s t r a c tThe kinetics of the dual fluorescence of several derivatives of dimethylaminobenzonitrile (DMABN) has been compared using fs-fluorescence upconversion experiments. Variation of the size and twist angle of the donor (dialkylamino group) suggest a large amplitude solvent-viscosity controlled diffusional twisting motion towards larger twist angles as the rate limiting step.Large rate differences were observed for an ester group as acceptor. Temperature dependent studies indicate that these differences are not connected with different activation barriers but with changes in the Arrhenius preexponential factor. It is argued that conical intersections along the reaction path can bring about these entropy changes.

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supporting

confidence: 91%

Section: Comparison Of Derivatives With Variation Of the Donor Group mentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Entropic effects in excited state CT reactions

Pigliucci

Vauthey

Rettig

2009

Chemical Physics Letters

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“…Since in these experiments the energetics of binding electrons are probed, it is impossible to deduce the atom positions during structural transitions without knowledge of the PES. Normally, the observed transient spectroscopic bands in the ultraviolet/visible range are very broad and even TR vibrational (IR) spectroscopy cannot cover the whole frequency range necessary for a complete structure determination [2]. Experimental results in ultrafast spectroscopy also raise the question whether ultrafast motions on the excited state PES can be described within the BornOppenheimer approximation [3] or whether one has to go beyond [4].…”

mentioning

confidence: 99%

Picosecond X-Ray Diffraction Probed Transient Structural Changes in Organic Solids

2001

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In this Letter, we report on the experimental characterization of the geometry of short-lived electronically excited states in organic solids by time-resolved x-ray diffraction. Here, the structure factor of the organic crystal is measured as a function of time. Since this technique gives complete structural information, it is a very useful tool for learning more about atom motions on the excited-state energy surface -"beyond" the broad band typical of conventional spectroscopy. Although we used molecular crystals rather than free molecules, the compounds show detectable transient structural changes on the ps to ns time scale in our study.

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Fast and Ultrafast Time‐Resolved Mid‐Infrared Spectrometry Using Lasers

Grills

George

2001

Handbook of Vibrational Spectroscopy

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The sections in this article are Introduction Fast TRIR Spectroscopy Fast TRIR Spectroscopy Using IR Lasers CW CO Lasers CW CO 2 Lasers Tunable IR Diode Lasers Color Center Lasers Difference Frequency Generation Ultrafast TRIR Studies Two‐Dimensional IR Spectroscopy Conclusions

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Excited state structure of 4-(dimethylamino)benzonitrile studied by femtosecond mid-infrared spectroscopy and ab initio calculations

Cited by 101 publications

References 24 publications

Entropic effects in excited state CT reactions

Entropic effects in excited state CT reactions

Picosecond X-Ray Diffraction Probed Transient Structural Changes in Organic Solids

Fast and Ultrafast Time‐Resolved Mid‐Infrared Spectrometry Using Lasers

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