Quantum Effects in Cold Molecular Collisions from Spatial Polarization of Electronic Wave Function

Bhattacharya, Debarati; Pawlak, Mariusz; Ben‐Asher, Anael; Landau, Arie; Haritan, Idan; Narevicius, Edvardas; Moiseyev, Nimrod

doi:10.1021/acs.jpclett.8b03807

Cited by 18 publications

(27 citation statements)

References 61 publications

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“… 46 , 47 This technique has been recently successfully applied for the He(1s2p, 3 P 2 ) + H 2 system. 62 It enables one to reduce the complexity of the problem enhancing the computational performance without losing physical essence. Within AVT, we represent the potential ( eq 3 ) in a basis set consisting of many angular functions.…”

Section: Computational Detailsmentioning

confidence: 99%

Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms

Pawlak

Żuchowski

Moiseyev

et al. 2020

J. Chem. Theory Comput.

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Cold collisions serve as a sensitive probe of the interaction potential. In the recent study of Klein et al. ( Nature Phys. 2017 , 13 , 35–38), the one-parameter scaling of the interaction potential was necessary to obtain agreement between theoretical and observed patterns of the orbiting resonances for excited metastable helium atoms colliding with hydrogen molecules. Here, we show that the effect of nonrigidity of the H 2 molecule on the resonant structure, absent in the previous study, is critical to predict the correct positions of the resonances in that case. We have complemented the theoretical description of the interaction potential and revised reaction rate coefficients by proper inclusion of the flexibility of the molecule. The calculated reaction rate coefficients are in remarkable agreement with the experimental data without empirical adjustment of the interaction potential. We have shown that even state-of-the-art calculations of the interaction energy cannot ensure agreement with the experiment if such an important physical effect as flexibility of the interacting molecule is neglected. Our findings about the significance of the nonrigidity effects can be especially crucial in cold chemistry, where the quantum nature of molecules is pronounced.

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Section: Computational Detailsmentioning

confidence: 99%

Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms

Pawlak

Żuchowski

Moiseyev

et al. 2020

J. Chem. Theory Comput.

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“…The possibility to isolate the resonances from the other states in the quasi-continuum can be utilized to calculate the resonance widths. See for example, the calculation of resonance widths (inverse lifetimes) and energies for

methods [ 48 ], spherical-box quantization [ 49 ] and from the analytical continuation of real stabilization graphs, utilizing a Gaussian basis [ 19 , 20 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 ]. This is the primary result of our work, demonstrating that resonances can be calculated from stabilization graphs obtained by utilizing grid methods and not only by applying basis sets, as previously done.…”

Section: Illustrative Numerical Examples For the Calculations Of Energies And Widths Of Resonancesmentioning

confidence: 99%

Variational Solutions for Resonances by a Finite-Difference Grid Method

et al. 2021

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We demonstrate that the finite difference grid method (FDM) can be simply modified to satisfy the variational principle and enable calculations of both real and complex poles of the scattering matrix. These complex poles are known as resonances and provide the energies and inverse lifetimes of the system under study (e.g., molecules) in metastable states. This approach allows incorporating finite grid methods in the study of resonance phenomena in chemistry. Possible applications include the calculation of electronic autoionization resonances which occur when ionization takes place as the bond lengths of the molecule are varied. Alternatively, the method can be applied to calculate nuclear predissociation resonances which are associated with activated complexes with finite lifetimes.

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“…24 Moreover, RVP was even used to calculate the He * −H 2 complex potential energy surfaces (CPESs) in order to interpret and describe cold molecular collision experiments, [25][26][27] these CPESs were used to compute theoretical cross sections that were in remarkable agreement with the measurements. 28,29 Additionally, RVP was also used for predicting the interatomic Coulombic decay (ICD) products within the extreme Li-He system. 30,31 In light of the above, it is of great interest in treating large chemical system.…”

Section: Introductionmentioning

confidence: 99%

Complex Energies and Transition-Dipoles for the Uracil anion Shape-type Resonances from stabilization curves via Padé

Bouskila

Landau

Haritan

et al. 2022

Preprint

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Absorption of slow moving electrons by neutral ground state nucleobases have been known to produce resonance, metastable, states. There are indications that such metastable states may play a key-role in DNA/RNA damage. Therefore, herein, we present an ab-initio, non-Hermitian investigation of the resonance positions and decay rates of the low lying shape-type states of the uracil anion. In addition, we calculate the complex transition dipoles between these resonance states. We employ the resonance via Padé (RVP) method to calculate these complex properties from real stabilization curves by analytical dilation into the complex plane. This method has al-ready been successfully applied to many small molecular systems and herein we present the first application of RVP to a medium-size system. The presented resonance energies are converged with respect to the size of the basis set and compared with previous theoretical works and experimental findings. Complex transition dipoles between the shape-type resonances are computed using the energy-converged basis set. The ability to calculate ab-initio energies and lifetimes of biologically relevant systems opens the door for studying reactions of such systems in which autoionization takes place. While the ability to also calculate their complex transition dipoles open the door for studying photo induced dynamics of such biological molecules.

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Quantum Effects in Cold Molecular Collisions from Spatial Polarization of Electronic Wave Function

Cited by 18 publications

References 61 publications

Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms

Evidence of Nonrigidity Effects in the Description of Low-Energy Anisotropic Molecular Collisions of Hydrogen Molecules with Excited Metastable Helium Atoms

Variational Solutions for Resonances by a Finite-Difference Grid Method

Complex Energies and Transition-Dipoles for the Uracil anion Shape-type Resonances from stabilization curves via Padé

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