Accurate quantum-mechanical rate constants for a linear response Azzouz-Borgis proton transfer model employing the multilayer multiconfiguration time-dependent Hartree approach

Craig, Ian R.; Thoss, Michael; Wang, Haobin

doi:10.1063/1.3624342

Cited by 30 publications

(20 citation statements)

References 56 publications

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“…No exact benchmark rate exists for this system, although multi-layer MCTDH calculations have been performed on a system-bath model designed to emulate this reaction 131,132 . The rate constant obtained from this procedure was 9.3 × 10 10 s –1 , which is in better agreement with QI than RPMD.…”

Section: The Azzouz-borgis Model For Proton Transfer In Polar Solventmentioning

confidence: 94%

Kinetic isotope effects and how to describe them

Karandashev

Meuwly

et al. 2017

Structural Dynamics

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We review several methods for computing kinetic isotope effects in chemical reactions including semiclassical and quantum instanton theory. These methods describe both the quantization of vibrational modes as well as tunneling and are applied to the ⋅H + H2 and ⋅H + CH4 reactions. The absolute rate constants computed with the semiclassical instanton method both using on-the-fly electronic structure calculations and fitted potential-energy surfaces are also compared directly with exact quantum dynamics results. The error inherent in the instanton approximation is found to be relatively small and similar in magnitude to that introduced by using fitted surfaces. The kinetic isotope effect computed by the quantum instanton is even more accurate, and although it is computationally more expensive, the efficiency can be improved by path-integral acceleration techniques. We also test a simple approach for designing potential-energy surfaces for the example of proton transfer in malonaldehyde. The tunneling splittings are computed, and although they are found to deviate from experimental results, the ratio of the splitting to that of an isotopically substituted form is in much better agreement. We discuss the strengths and limitations of the potential-energy surface and based on our findings suggest ways in which it can be improved.

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Section: The Azzouz-borgis Model For Proton Transfer In Polar Solventmentioning

confidence: 94%

Kinetic isotope effects and how to describe them

Karandashev

Meuwly

et al. 2017

Structural Dynamics

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“…30 Through their work, Vendrell and Meyer 30 showed that (i) the Heidelberg ML-MCTDH implementation works correctly and (ii) ML-MCTDH is indeed much superior to MCTDH for treating large systems (more than 15D, say). In particular, if there are many weakly coupled modes, ML-MCTDH performs excellently, allowing the treatment of hundreds of DOFs as shown already by Thoss, Wang, and their coworkers 28,[32][33][34][35]44 as well as by Manthe and his co-workers. 36 Now let us outline the route from the standard wavepacket propagation method over the MCTDH algorithm to ML-MCTDH.…”

Section: B the Multilayer Multiconfiguration Time-dependent Hartree mentioning

confidence: 99%

Full dimensional quantum-mechanical simulations for the vibronic dynamics of difluorobenzene radical cation isomers using the multilayer multiconfiguration time-dependent Hartree method

Meng

Faraji

Vendrell

et al. 2012

The Journal of Chemical Physics

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Full dimensional multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) calculations of the dynamics of the three difluorobenzene cationic isomers in five lowest-lying doublet electronic states using the ab initio multistate multimode vibronic coupling Hamiltonian (MMVCH) model are carried out using the Heidelberg MCTDH package. The same dynamical problems, but treated with the MCTDH scheme and using a reduced dimensional ab initio MMVCH model, have been previously reported [S. Faraji, H.-D. Meyer, and H. Köppel, "Multistate vibronic interactions in difluorobenzene radical cations. II Quantum dynamical simulations," J. Chem. Phys. 129, 074311 (2008)]. For easy comparison with the reduced dimensional results, 11D or 10D ML-MCTDH calculations are also performed. Extensive ML-MCTDH test calculations are performed to find appropriate ML-MCTDH wavefunction structures (ML-trees), and the convergence of the ML-MCTDH calculations are carefully checked to ensure accurate results. Based on the appropriate ML-trees, the photoelectron (PE) spectrum and the mass analyzed threshold ionization (MATI) spectrum are simulated, analyzed, and compared with corresponding experimental spectra. Because of its efficient simulation capability for large systems, ML-MCTDH calculations save a considerable amount of central processing unit (CPU)-time, even when a reduced dimensional MMVCH is used, i.e., the same reduced model as in the corresponding MCTDH calculations. Simulations of the experimental PE spectra by full dimensional ML-MCTDH calculations reproduced main peaks, which originate from different electronic states. The agreement is improved as compared to the reduced dimensionality calculations. Unfortunately, the experimental PE spectra are not very well resolved. Therefore, we compare our calculations additionally with highly resolved MATI spectra, which, however, are only available for the X̃ state. Based on a series of ML-MCTDH simulations with longer propagation time for X̃, a number of vibrational modes, including fundamentals, their combinations, and overtones are simulated and assigned by comparing with the experimental assignments and the ab initio frequencies. Excellent correlation between the experimental and full dimensional ML-MCTDH results show that ML-MCTDH is accurate and very efficient and that the ab initio MMVCH model is very suitable for ML-MCTDH calculations.

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“…In this case, one may apply the ML-MCTDH method to calculate the reactive flux correlation function and then obtain the rate constant. Examples for application of the ML-MCTDH method to such processes include the calculation of rates for electron transfer 106 as well as proton transfer 107 reactions.…”

Section: C)mentioning

confidence: 99%

Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups

Wang

Persson

et al. 2012

The Journal of Chemical Physics

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Photoinduced electron transfer processes in perylene-titanium dioxide dye-semiconductor systems are studied. In particular, the influence of saturated and unsaturated aliphatic spacer groups inserted between the chromophore and the semiconductor substrate is investigated. The study is based on a recently developed method that combines first-principles electronic structure calculations to characterize the dye-semiconductor systems and accurate multilayer multiconfiguration time-dependent Hartree simulations to reveal the underlying nonadiabatic dynamics. The results show that, in agreement with previous experimental studies, the spacer groups may affect the electron transfer dynamics significantly. Furthermore, the influence of electronic-vibrational coupling on the electron transfer dynamics and absorption spectra is discussed.

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Accurate quantum-mechanical rate constants for a linear response Azzouz-Borgis proton transfer model employing the multilayer multiconfiguration time-dependent Hartree approach

Cited by 30 publications

References 56 publications

Kinetic isotope effects and how to describe them

Kinetic isotope effects and how to describe them

Full dimensional quantum-mechanical simulations for the vibronic dynamics of difluorobenzene radical cation isomers using the multilayer multiconfiguration time-dependent Hartree method

Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups

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