Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userQuantum Monte Carlo Investigation of the H-transfer Reaction of Criegee Intermediate CH3CHOO: A Benchmark Calculation
444
0
0.0
(
0
)
Authors
Zhiping Wang School of Physics
Ask ChatGPT about the research
No Arabic abstract
We perform the fixed-node diffuse Monte Carlo (FN DMC) calculations to determine the barrier height and reaction energy of a critical reaction, the H-transfer reaction from syn-CH3CHOO to vinyl hydroperoxide. The FN DMC barrier height is found to be 16.60+/-0.35 kcal/mol which agrees well with the experimental measurement within a few tenths of kcal, justifying the reliability of the FN DMC method for predicting barrier height of the rapid unimolecular reaction of Criegee intermediates. By comparing the predictions from the CCSD(t), G3 (MCG3), DFT and MP2 methods with respect to the FN DMC results and available experiment measurement, we found that the CCSD(t) barrier heights agree with the FN DMC counterpart within statistical errors, and is within a closer agreement with experiment and FN DMC prediction than the G3(MCG3) models. Barrier heights predicted from the relatively more economic DFT methods are within a few tenths kcal of the FN DMC prediction. MP2 method severely underestimates the barrier height. FN DMC prediction for the reaction energy is -17.25+/-0.31 kcal/mol, setting an upper limit for the reaction energies predicted by the post Hartree-Fock methods and a lower limit for the DFT reaction energies. We provide FN DMC input for clarifying the energetic uncertainties in the critical H-transfer reaction of syn-CH3CHOO. The quantitatively close agreements between the FN DMC barrier height and experimental measurement, and between the predictions from the FN DMC and G3 model for the reaction energy provide a theoretical basis for resolving the energy uncertainty in this reaction.
rate research
Read More
The H + D_2^+(v=0,1 and 2) charge transfer reaction is studied using an accurate wave packet method, using recently proposed coupled diabatic potential energy surfaces. The state-to-state cross section is obtained for three different channels: non-reactive charge transfer, reactive charge transfer, and exchange reaction. The three processes proceed via the electronic transition from the first excited to the ground electronic state. The cross section for the three processes increases with the initial vibrational excitation. The non-reactive charge transfer process is the dominant channel, whose branching ratio increases with collision energy, and it compares well with experimental measurements at collision energies around 0.5 eV. For lower energies the experimental cross section is considerably higher, suggesting that it corresponds to higher vibrational excitation of D_2^+(v) reactants. Further experimental studies of this reaction and isotopic variants are needed, where conditions are controlled to obtain a better analysis of the vibrational effects of the D_2^+ reagents.
The non-adiabatic quantum dynamics of the H+H$_2^+$ $rightarrow$ H$_2$+ H$^+$ charge transfer reactions, and some isotopic variants, is studied with an accurate wave packet method. A recently developed $3times$3 diabatic potential model is used, which is based on very accurate {it ab initio} calculations and includes the long-range interactions for ground and excited states. It is found that for initial H$_2^+$(v=0), the quasi-degenerate H$_2$(v=4) non-reactive charge transfer product is enhanced, producing an increase of the reaction probability and cross section. It becomes the dominant channel from collision energies above 0.2 eV, producing a ratio, between v=4 and the rest of vs, that increases up to 1 eV. H+H$_2^+$ $rightarrow$ H$_2^+$+ H exchange reaction channel is nearly negligible, while the reactive and non-reactive charge transfer reaction channels are of the same order, except that corresponding to H$_2$(v=4), and the two charge transfer processes compete below 0.2 eV. This enhancement is expected to play an important vibrational and isotopic effect that need to be evaluated. For the three proton case, the problem of the permutation symmetry is discussed when using reactant Jacobi coordinates.
We present a variational MonteCarlo (VMC) and lattice regularized diffusion MonteCarlo (LRDMC) study of the binding energy and dispersion curve of the water dimer. As a variation ansatz we use the JAGP wave function, an implementation of the resonating valence bond (RVB) idea. Actually one the aim of the present work is to investigate how the bonding of two water molecules, as a prototype of the hydrogen-bonded complexes, could be described within an JAGP approach. Using a pseudopotential for the inert core of the Oxygen, with a full optimization of the variational parameters, we obtain at the VMC level a binding energy of -4.5(0.1) Kcal/mol, while LRDMC calculations gives -4.9(0.1) Kcal/mol (experiment 5 Kcal/Mol). The calculated dispersion curve reproduces both at the VMC and LRDMC level the miminum position and the curvature.The quality of the WF gives us the possibility to dissect the binding energy in different contributions by appropriately switching off determinantal and Jastrow terms in the JAGP: we estimate the dynamical contribution to the binding energy to be of the order of 1.4(0.2) Kcal/Mol whereas the covalent contribution about 1.0(0.2) Kcal/Mol. JAGP reveales thus a promising WF for describing systems where both dispersive and covalent forces play an important role.
We present a simple interpolation formula for the rate of an electron transfer reaction as a function of the electronic coupling strength. The formula only requires the calculation of Fermi Golden Rule and Born-Oppenheimer rates and so can be combined with any methods that are able to calculate these rates. We first demonstrate the accuracy of the formula by applying it to a one dimensional scattering problem for which the exact quantum mechanical, Fermi Golden Rule, and Born-Oppenheimer rates are readily calculated. We then describe how the formula can be combined with the Wolynes theory approximation to the Golden Rule rate, and the ring polymer molecular dynamics (RPMD) approximation to the Born-Oppenheimer rate, and used to capture the effects of nuclear tunnelling, zero point energy, and solvent friction on condensed phase electron transfer reactions. Comparison with exact hierarchical equations of motion (HEOM) results for a demanding set of spin-boson models shows that the interpolation formula has an error comparable to that of RPMD rate theory in the adiabatic limit, and that of Wolynes theory in non-adiabatic limit, and is therefore as accurate as any method could possibly be that attempts to generalise these methods to arbitrary electronic coupling strengths.
We investigate the viability of the phaseless finite temperature auxiliary field quantum Monte Carlo (ph-FT-AFQMC) method for ab initio systems using the uniform electron gas as a model. Through comparisons with exact results and finite temperature coupled cluster theory, we find that ph-FT-AFQMC is sufficiently accurate at high to intermediate electronic densities. We show both analytically and numerically that the phaseless constraint at finite temperature is fundamentally different from its zero temperature counterpart (i.e., ph-ZT-AFQMC) and generally one should not expect ph-FT-AFQMC to agree with ph-ZT-AFQMC in the low temperature limit. With an efficient implementation, we are able to compare exchange-correlation energies to existing results in the thermodynamic limit and find that existing parameterizations are highly accurate. In particular, we found that ph-FT-AFQMC exchange-correlation energies are in a better agreement with a known parametrization than is restricted path-integral Monte Carlo in the regime of $Thetale0.5$ and $r_s le 2$, which highlights the strength of ph-FT-AFQMC.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
