Mode specific dynamics in multichannel reaction NH+ + H2

2021 ◽  
Author(s):  
Weiliang Shi ◽  
Kun Wang ◽  
Ping Zhang ◽  
Le Yu ◽  
Anyang Li
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Energy Surface ◽  
Initial State ◽  
Rotational Mode ◽  
Mode Specificity

The vibrational and rotational mode specificity of the multichannel NH+ + H2 reaction is studied on a recently constructed ab initio based global potential energy surface using an initial state...

SEVEN-DIMENSIONAL QUANTUM DYNAMICS STUDY OF THE H2 + NH2 → H + NH3 REACTION ON AN INTERPOLATED POTENTIAL ENERGY SURFACE

2013 ◽  
Vol 12 (06) ◽  
pp. 1350054 ◽  
Author(s):  
YANG YANG ◽  
RUI LIU ◽  
RENZHUO WAN ◽  
MINGHUI YANG
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Cross Sections ◽  
Rate Constants ◽  
Quantum Dynamics ◽  
Energy Surface ◽  
Dimensional Model ◽  
Initial State ◽  
Wave Packet Dynamics

Initial-state-selected time-dependent wave packet dynamics studies have been performed for the H 2 + NH 2 → H + NH 3 reaction with a seven-dimensional model on a new interpolated ab initio potential energy surface (PES). The PES is constructed using modified Shepard interpolation Scheme and contains 1967 data points with ab initio calculations carried out on UCCSD(T)/aug-cc-pVTZ level. In the seven-dimensional model, NH 2 group keeps C2v symmetry and two NH bonds are fixed at their equilibrium values. The total reaction probabilities are calculated when (1) the two reactants are initially at their ground states; (2) NH 2 bending mode is excited, and (3) H 2 is on its first vibrational excited state. The integral cross sections are also reported for these initial states with centrifugal-sudden approximation. Thermal rate constants are calculated for the temperature range of 200–2000 K and compared with the previous calculated values and available experimental data. Good agreements between theory and experiments for the rate constants at intermediate temperature are achieved on this PES.

Active Learning Accelerates Ab Initio Molecular Dynamics on Pericyclic Reactive Energy Surfaces

2020 ◽  
Author(s):  
Shi Jun Ang ◽  
Wujie Wang ◽  
Daniel Schwalbe-Koda ◽  
Simon Axelrod ◽  
Rafael Gomez-Bombarelli
Keyword(s):  
Molecular Dynamics ◽  
Potential Energy ◽  
Transition State ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Energy Surface ◽  
Computational Cost ◽  
Reactive Trajectories ◽  
Dynamics Simulations ◽  
Energy Surfaces

<div>Modeling dynamical effects in chemical reactions, such as post-transition state bifurcation, requires <i>ab initio</i> molecular dynamics simulations due to the breakdown of simpler static models like transition state theory. However, these simulations tend to be restricted to lower-accuracy electronic structure methods and scarce sampling because of their high computational cost. Here, we report the use of statistical learning to accelerate reactive molecular dynamics simulations by combining high-throughput ab initio calculations, graph-convolution interatomic potentials and active learning. This pipeline was demonstrated on an ambimodal trispericyclic reaction involving 8,8-dicyanoheptafulvene and 6,6-dimethylfulvene. With a dataset size of approximately</div><div>31,000 M062X/def2-SVP quantum mechanical calculations, the computational cost of exploring the reactive potential energy surface was reduced by an order of magnitude. Thousands of virtually costless picosecond-long reactive trajectories suggest that post-transition state bifurcation plays a minor role for the reaction in vacuum. Furthermore, a transfer-learning strategy effectively upgraded the potential energy surface to higher</div><div>levels of theory ((SMD-)M06-2X/def2-TZVPD in vacuum and three other solvents, as well as the more accurate DLPNO-DSD-PBEP86 D3BJ/def2-TZVPD) using about 10% additional calculations for each surface. Since the larger basis set and the dynamic correlation capture intramolecular non-covalent interactions more accurately, they uncover longer lifetimes for the charge-separated intermediate on the more accurate potential energy surfaces. The character of the intermediate switches from entropic to thermodynamic upon including implicit solvation effects, with lifetimes increasing with solvent polarity. Analysis of 2,000 reactive trajectories on the chloroform PES shows a qualitative agreement with the experimentally-reported periselectivity for this reaction. This overall approach is broadly applicable and opens a door to the study of dynamical effects in larger, previously-intractable reactive systems.</div>

Rotational de-excitations of C3H+ (1Σ+) by collision with He: new ab initio potential energy surface and scattering calculations

2020 ◽  
Vol 494 (4) ◽  
pp. 5675-5681 ◽  
Author(s):  
Sanchit Chhabra ◽  
T J Dhilip Kumar
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Cross Sections ◽  
Energy Surface ◽  
Molecular Ions ◽  
Basis Set ◽  
Rate Coefficients ◽  
Close Coupling ◽  
Collisional Rate Coefficients

ABSTRACT Molecular ions play an important role in the astrochemistry of interstellar and circumstellar media. C3H+ has been identified in the interstellar medium recently. A new potential energy surface of the C3H+–He van der Waals complex is computed using the ab initio explicitly correlated coupled cluster with the single, double and perturbative triple excitation [CCSD(T)-F12] method and the augmented correlation consistent polarized valence triple zeta (aug-cc-pVTZ) basis set. The potential presents a well of 174.6 cm−1 in linear geometry towards the H end. Calculations of pure rotational excitation cross-sections of C3H+ by He are carried out using the exact quantum mechanical close-coupling approach. Cross-sections for transitions among the rotational levels of C3H+ are computed for energies up to 600 cm−1. The cross-sections are used to obtain the collisional rate coefficients for temperatures T ≤ 100 K. Along with laboratory experiments, the results obtained in this work may be very useful for astrophysical applications to understand hydrocarbon chemistry.

Dynamics and kinetics of the Si(1D) + H2/D2 reactions on a new global ab initio potential energy surface

2021 ◽  
Vol 23 (10) ◽  
pp. 6141-6153
Author(s):  
Jianwei Cao ◽  
Yanan Wu ◽  
Haitao Ma ◽  
Zhitao Shen ◽  
Wensheng Bian
Keyword(s):  
Molecular Dynamics ◽  
Potential Energy ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Quantum Dynamics ◽  
Energy Surface ◽  
Molecular Dynamics Calculations ◽  
Ring Polymer ◽  
Ring Polymer Molecular Dynamics ◽  
Kinetics Of

Quantum dynamics and ring polymer molecular dynamics calculations reveal interesting dynamical and kinetic behaviors of an endothermic complex-forming reaction.

scholarly journals Variational analysis of HF dimer tunneling rotational spectra using an ab initio potential energy surface

2021 ◽  
pp. 111481
Author(s):  
Oleg L. Polyansky ◽  
Roman I. Ovsyannikov ◽  
Jonathan Tennyson ◽  
Sergei P. Belov ◽  
Mikhail Yu. Tretyakov ◽  
...  
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Variational Analysis ◽  
Energy Surface ◽  
Rotational Spectra

An analytical six‐dimensional potential energy surface for (HF)2 from ab initio calculations

1988 ◽  
Vol 89 (5) ◽  
pp. 3002-3007 ◽  
Author(s):  
P. R. Bunker ◽  
Manfred Kofranek ◽  
Hans Lischka ◽  
Alfred Karpfen
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Energy Surface
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