arXiv subjects

Aleksandra M. Tucholska

Publications and source records attributed to Aleksandra M. Tucholska.

4 recordsLinked to original sources

arXiv2023

F-12 density matrices and cumulants from the explicitly connected coupled-cluster theory

We present the expansion to the expectation value coupled cluster theory (XCC) to the wavefunctions that include the inter electronic distances $r_{12}$ explicitly. We have extended our algebraic manipulation code \paldus to deal with the rems arising in the CC-F12 theory. We present the full working expressions for the one-electron density matrix (1RDM) and cumulant of the two-electron density matrix ($λ$-2RDM) in the framework of XCC-F12 theory. We discuss the possible approximations the expressions.

physics.chem-ph↗

arXiv2021

Molecular properties from the explicitly connected expressions of the response functions within the coupled-cluster theory

We review the methods based on expectation value coupled cluster formalism - a common framework for the derivation of properties: the ground-state average value of an observable, cumulants of the second-order reduced density matrices, polarization propagator, quadratic response function, and transition probabilities. We discuss the approximations and give examples of the most important numerical results.

physics.chem-ph↗

arXiv2017

Combining Slater-type orbitals and effective core potentials

We present a general methodology to evaluate matrix elements of the effective core potentials (ECPs) within one-electron basis set of Slater-type orbitals (STOs). The scheme is based on translation of individual STO distributions in the framework of Barnett-Coulson method. We discuss different types of integrals which naturally appear and reduce them to few basic quantities which can be calculated recursively or purely numerically. Additionally, we consider evaluation of the STOs matrix elements involving the core polarisation potentials (CPP) and effective spin-orbit potentials. Construction of the STOs basis sets designed specifically for use with ECPs is discussed and differences in comparison with all-electron basis sets are briefly summarised. We verify the validity of the present approach by calculating excitation energies, static dipole polarisabilities and valence orbital energies for the alkaline earth metals (Ca, Sr, Ba). Finally, we evaluate interaction energies, permanent dipole moments and ionisation energies for barium and strontium hydrides, and compare them with the best available experimental and theoretical data.

physics.chem-ph↗

arXiv2014

Transition properties from the Hermitian formulation of the coupled cluster polarization propagator

Theory of one-electron transition density matrices has been formulated within the time-independent coupled cluster method for the polarization propagator [R. Moszynski, P. S. Żuchowski, and B. Jeziorski, Coll. Czech. Chem. Commun. {\bf 70}, 1109 (2005)]. Working expressions have been obtained and implemented with the coupled cluster method limited to single, double, and linear triple excitations (CC3). Selected dipole and quadrupole transition probabilities of the alkali earth atoms, computed with the new transition density matrices are compared to the experimental data. Good agreement between theory and experiment is found. The results obtained with the new approach are of the same quality as the results obtained with the linear response coupled cluster theory (LRCC). The one-electron density matrices for the ground state in the CC3 approximation have also been implemented. The dipole moments for a few representative diatomic molecules have been computed with several variants of the new approach, and the results are discussed to choose the approximation with the best balance between the accuracy and computational efficiency.

physics.chem-ph↗