Including tunneling into the classical cross sections and rate constants for the N(2D) + H2 (v = 0, j = 0) reaction

Larrégaray, P.; Bonnet, Laurent

doi:10.1007/s00214-021-02749-6

Cited by 2 publications

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“…Transition state theory (TST) is a clever rate constant approximation that avoids dynamics simulations and delivers rates in terms of static thermodynamics information. , Since TST is a classical mechanics theory, early theories based on one-dimensional potential approximation were elaborated to account for quantum tunneling, such as Wigner or Eckart corrections. , Nowadays, more sophisticated approximations have been developed to include, at least to some extent, the effects neglected by 1D approaches to tunneling corrections and limitations of the TST method itself, such as corner cutting, nonseparability of the reaction coordinate, and recrossing. − …”

Section: Introductionmentioning

confidence: 99%

Heavy Atom Tunneling in Organic Reactions at Coupled Cluster Potential Accuracy with a Parallel Implementation of Anharmonic Constant Calculations and Semiclassical Transition State Theory

Mandelli

Aieta

Ceotto

2022

J. Chem. Theory Comput.

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We describe and test on some organic reactions a parallel implementation strategy to compute anharmonic constants, which are employed in semiclassical transition state theory reaction rate calculations. Our software can interface with any quantum chemistry code capable of a single point energy estimate, and it is suitable for both minimum and transition state geometry calculations. After testing the accuracy and comparing the efficiency of our implementation against other software, we use it to estimate the semiclassical transition state theory (SCTST) rate constant of three reactions of increasing dimensionality, known as examples of heavy atom tunneling. We show how our method is improved in efficiency with respect to other existing implementations. In conclusion, our approach allows SCTST rates and heavy atom tunneling at a high level of electronic structure theory (up to CCSD(T)) to be evaluated. This work shows how crucial the possibility to perform high level ab initio rate evaluations can be.

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Section: Introductionmentioning

confidence: 99%

Heavy Atom Tunneling in Organic Reactions at Coupled Cluster Potential Accuracy with a Parallel Implementation of Anharmonic Constant Calculations and Semiclassical Transition State Theory

Mandelli

Aieta

Ceotto

2022

J. Chem. Theory Comput.

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Vibrational spectroscopy simulation of solvation effects on a G-quadruplex

Moscato

Gabas

Conte

et al. 2023

Journal of Biomolecular Structure and Dynamics

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It is commonly believed that solvation of a polar molecule in a polar solvent has the only effect of red shifting all of his spectroscopical features, similarly solvating a polar molecule in a non polar solvent has the opposite effect. Naturally this can be retained valid for very simple molecular systems, but what are the effects of solvation to more complex molecular systems ?. A theoretical analysis of different kind of systems can be helpful to give atomistic insights to answer these questions, and also help develope a model which can be used to take in consideration solvation effects for complex kind of molecular systems. With this work [1] our goal is to try to understand the effects of solvation on vibrational features, in particular our work focuses on the differences that occurs between gas phase spectroscopic simulations and simulations carried on in a box of solvent. The latest one should also permit us to show that the use of an appropriate explicit solvent in this kind of simulations, is fundamental to catch the right shifts [2] caused by interaction of the system with the solvent molecule. We started our work with a simple molecule of 2'-deoxyguanosine, the informations gained from the first set of simulations has been used to show how solvation acts differently when the same molecule is found in a quadruplex geometry. In the end we will also show how the use of both classical and semiclassical [3] approaches combined with the use of Force Fields, [4,5] are able to give a good qualitative reproduction of experimental data.

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Including tunneling into the classical cross sections and rate constants for the N(2D) + H2 (v = 0, j = 0) reaction

Abstract: Including tunneling into the classical cross sections and rate constants for the N( 2 D)+H2 (v=0, j=0) reaction

Cited by 2 publications

References 50 publications

Heavy Atom Tunneling in Organic Reactions at Coupled Cluster Potential Accuracy with a Parallel Implementation of Anharmonic Constant Calculations and Semiclassical Transition State Theory

Heavy Atom Tunneling in Organic Reactions at Coupled Cluster Potential Accuracy with a Parallel Implementation of Anharmonic Constant Calculations and Semiclassical Transition State Theory

Vibrational spectroscopy simulation of solvation effects on a G-quadruplex

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