Femtosecond time-resolved dynamics of the electronically excited ethylene molecule

Stert, V.; Lippert, H.; Ritze, H.‐H.; Radloff, W.

doi:10.1016/j.cplett.2004.02.077

Cited by 45 publications

(68 citation statements)

References 13 publications

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“…As ethylene is the simplest molecule with a C=C double bond, it has been extensively studied both experimentally and computationally. 22,[50][51][52][53][54][55][56][57][58] The AIMC and AIMS simulations were carried out with a modified version of AIMS-MOLPRO, 36 which was extended to include Ehrenfest dynamics for the TBFs. Electronic structure calculations were performed with the CASSCF method using an active space of two electrons in two orbitals and equally weighted stateaveraging over the three lowest singlet states, i.e., SA-3-CAS(2/2).…”

Section: Computational Details and Resultsmentioning

confidence: 99%

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

Makhov

Glover

Martı́nez

et al. 2014

The Journal of Chemical Physics

188

244

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An atomic orbital-based formulation of analytical gradients and nonadiabatic coupling vector elements for the state-averaged complete active space self-consistent field method on graphical processing units We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as "cloning," in analogy to the "spawning" procedure in AIMS. This synthesis of AIMS and MCE allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, "trains," as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.

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Section: Computational Details and Resultsmentioning

confidence: 99%

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

Makhov

Glover

Martı́nez

et al. 2014

The Journal of Chemical Physics

188

244

View full text Add to dashboard Cite

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“…Therefore we found no evidence for a fast excitedstate dissociation channel. As a more sensitive method to investigate the possible existence or absence of this pathway, we suggest resonant ionization of H atoms 36 or ethene 37 as the probe step, because otherwise small product yields might remain undetected.…”

Section: Resultsmentioning

confidence: 99%

Excited-state decay of hydrocarbon radicals, investigated by femtosecond time-resolved photoionization: Ethyl, propargyl, and benzyl

Zierhut

Noller

Schultz

et al. 2005

The Journal of Chemical Physics

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The excited state decay of the hydrocarbon radicals ethyl, C 2 H 5 ; propargyl, C 3 H 3 ; and benzyl, C 7 H 7 was investigated by femtosecond time-resolved photoionization. Radicals were generated by flash pyrolysis of n-propyl nitrite, propargyl bromide, and toluene, respectively. It is shown that the 2 2 AЈ ͑3s͒ Rydberg state of ethyl excited at 250 nm decays with a time constant of 20 fs. No residual signal was observed at longer delay times. For the 3 2 B 1 state of propargyl excited at 255 nm a slower decay with a time constant 50± 10 fs was determined. The 4 2 B 2 state of benzyl excited at 255 nm decays within 150± 30 fs.

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“…They are shown in Fig. 2(b) and can be rationalized analogously to the data from CPDMe 6 (for the absorption spectrum of CPDMe 4 PrH see the ESI †). In addition to the photoelectron bands which were reported earlier, a weak band of longer life time is found in the [1,1 0 ] regime.…”

Section: Experimental Trpesmentioning

confidence: 96%

“…Although the TRPES data for CPD and its derivatives were earlier analyzed via a biexponential fit, 9,10 we here show on the example of CPDMe 4 PrH that the dynamics can be described equally well via a single exponential decay and a shift in time zero or a fit according to eqn (4). The most appropriate model can only be chosen with the help of the theoretical knowledge of the underlying dynamics and the direct simulations of observables.…”

Section: Generalization To Other Polyenesmentioning

confidence: 99%

“…This is especially important because a profound understanding of photoinduced dynamics almost always necessitates a detailed comparison of experiment with theory. Many model systems have been investigated by time-resolved experiments [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] or dynamical simulations. [20][21][22][23][24][25][26] We believe that fundamental questions could be answered more easily by joint studies connecting experimental approaches with such simulations.…”

Section: Introductionmentioning

confidence: 99%

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Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

Wolf

Kuhlman

Schalk

et al. 2014

Phys. Chem. Chem. Phys.

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Femtosecond time-resolved dynamics of the electronically excited ethylene molecule

Cited by 45 publications

References 13 publications

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

Excited-state decay of hydrocarbon radicals, investigated by femtosecond time-resolved photoionization: Ethyl, propargyl, and benzyl

Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

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