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Michal Hapka

Publications and source records attributed to Michal Hapka.

4 recordsLinked to original sources
arXiv2021

Symmetry-adapted perturbation theory based on multiconfigurational wave function description of monomers

We present a formulation of the multiconfigurational (MC) wave function symmetry-adapted perturbation theory (SAPT). The method is applicable to noncovalent interactions between monomers which require a multiconfigurational description, in particular when the interacting system is strongly correlated or in an electronically excited state. SAPT(MC) is based on one- and two-particle reduced density matrices of the monomers and assumes the single-exchange approximation for the exchange energy contributions. Second-order terms are expressed through response properties from extended random phase approximation (ERPA) equations. SAPT(MC) is applied either with generalized valence bond perfect pairing (GVB) or with complete active space self consistent field (CASSCF) treatment of the monomers. We discuss two model multireference systems: the H2-H2 dimer in out-of-equilibrium geometries and interaction between the argon atom and excited state of ethylene. In both cases SAPT(MC) closely reproduces benchmark results. Using the C2H4-Ar complex as an example, we examine second-order terms arising from negative transitions in the linear response function of an excited monomer. We demonstrate that the negative-transition terms must be accounted for to ensure qualitative prediction of induction and dispersion energies and develop a procedure allowing for their computation. Factors limiting the accuracy of SAPT(MC) are discussed in comparison with other second-order SAPT schemes on a data set of small single-reference dimers.

physics.chem-ph↗
arXiv2016

Employing Range Separation on the meta-GGA Rung: New Functional Suitable for Both Covalent and Noncovalent Interactions

We devise a scheme for converting an existing exchange functional into its range-separated hybrid variant. The underlying exchange hole of the Becke-Roussel type has the exact second-order expansion in the interelectron distance. The short-range part of the resulting range-separated exchange energy depends on the kinetic energy density and the Laplacian even if the base functional lacks the dependence on these variables. The most successful practical realization of the scheme, named LC-PBETPSS, combines the range-separated PBE exchange lifted to the hybrid meta-GGA rung and the TPSS correlation. The value of the range-separation parameter is estimated theoretically and confirmed by empirical optimization. The D3 dispersion correction is recommended for all energy computations employing the presented functional. Numerical tests show remarkably robust performance of the method for noncovalent interaction energies, barrier heights, main-group thermochemistry, and excitation energies.

physics.chem-ph↗
arXiv2015

Observation of orbiting resonances in He(3S1) + NH3 Penning ionization

Resonances are among the clearest quantum mechanical signatures of scattering processes. Previously, shape resonances and Feshbach resonances have been observed in inelastic and reactive collisions involving atoms or diatomic molecules. Structure in the integral cross section has been observed in a handful of elastic collisions involving polyatomic molecules. The present paper presents the observation of shape resonances in the reactive scattering of a polyatomic molecule, NH3. A merged-beam study of the gas phase He((3)S1) + NH3 Penning ionization reaction dynamics is described in the collision energy range 3.3 $μ$eV < E$_{coll}$ < 10 meV. In this energy range, the reaction rate is governed by long-range attraction. Peaks in the integral cross section are observed at collision energies of 1.8 meV and 7.3 meV and are assigned to $\ell = 15,16$ and $\ell = 20,21$ partial wave resonances, respectively. The experimental results are well reproduced by theoretical calculations with the short-range reaction probability P$_{sr}$ = 0.035. No clear signature of the orbiting resonances is visible in the branching ratio between NH3(+) and NH2(+) formation.

physics.chem-ph↗
arXiv2014

Dynamics of gas phase Ne$^*$ + NH$_3$ and Ne$^*$ + ND$_3$ Penning ionization at low temperatures

Two isotopic chemical reactions, $\mathrm{Ne}^*$ + NH$_3$, and $\mathrm{Ne}^*$ + ND$_3$, have been studied at low collision energies by means of a merged beams technique. Partial cross sections have been recorded for the two reactive channels, namely $\mathrm{Ne}^*$ + NH$_3$ $\rightarrow$ Ne + NH$_3^+$ + $e^-$, and $\mathrm{Ne}^*$ + NH$_3$ $\rightarrow$ Ne + NH$_2^+$ + H + $e^-$, by detecting the NH$_3^+$ and NH$_2^+$ product ions, respectively. The cross sections for both reactions were found to increase with decreasing collision energy, $E_{coll}$, in the range 8 $μ$eV$<E_{coll}<$ 20 meV. The measured rate constant exhibits a curvature in a log(k)-log($E_{coll}$) plot from which it is concluded that the Langevin capture model does not properly describe the $\mathrm{Ne}^*$ + NH$_3$ reaction in the entire range of collision energies covered here. Calculations based on multichannel quantum defect theory were performed to reproduce and interpret the experimental results. Good agreement was obtained by including long range van der Waals interactions combined with a 6-12 Lennard-Jones potential. The branching ratio between the two reactive channels, $Γ= \frac{[NH_2^+]}{[NH_2^+]+[NH_3^+]}$, is relatively constant, $Γ\approx 0.3$, in the entire collision energy range studied here. Possible reasons for this observation are discussed and rationalised in terms of relative time scales of the reactant approach and the molecular rotation. Isotopic differences between the $\mathrm{Ne}^*$ + NH$_3$ and $\mathrm{Ne}^*$ + ND$_3$ reactions are small, as suggested by nearly equal branching ratios and cross sections for the two reactions.

physics.chem-ph↗