Spójne wzbudzenia trzykrotne w metodzie sprzężonych klasterów w zastosowaniu do opisu stanów wzbudzonych w układach otwartopowłokowych

W obrębie zaprezentowanej pracy doktorskiej wyróżnić można trzy obszary. Jeden to opracowanie niezbędnych zagadnień teoretycznych, wyprowadzenie równań i stworzenie metody EOMCCSDT stosowalnej do stanów otwartopowłokowych. Drugim jest praca programistyczna, która polegała na wykonaniu programu realizującego obliczenia w oparciu o metodę EOMCCSDT. Ostatni obszar to praca aplikacyjna, której przedmiotem były obliczenia zrealizowane za pomocą stworzonego programu, dotyczące grupy układów otwartopowłokowych. Wykonany program jest dość efektywną implementacją. Na osiągnięcie tego celu złożyło się zastosowanie faktoryzacji równań zarówno w obrębie części realizującej obliczenia dla stanu podstawowego, jak i dla równań EOM. Dzięki temu zabiegowi rząd procedury obliczeniowej nie przekracza n8. Program jest stworzony przy użyciu takiej techniki programowania, aby zredukowane było zużycie pamięci RAM komputera, dzięki czemu można wykonywać obliczenia angażujące dużą liczbę orbitali molekularnych. W kluczowych dla szybkości programu fragmentach zostały wykorzystane reguły symetrii przestrzennej, co znacznie skraca czas obliczeń układów posiadających wysoką symetrię. Program posiada także bardzo efektywną procedurę związaną z tworzeniem wektorów startowych, dzięki czemu bardzo mało prawdopodobne jest nieznalezienie rozwiązania dla konkretnego stanu wzbudzonego. Program po zintegrowaniu z pakietem ACES II ma możliwość optymalizacji geometrii stanów wzbudzonych oraz obliczania częstości harmonicznych. Część aplikacyjna pracy dostarczyła wyników dowodzących efektywności metody. W zdecydowanej większości przypadków osiąga się bardzo dobrą zgodność z wartościami doświadczalnymi, sięgającą poniżej 0.1 eV. Prezentowane w pracy porównanie z rezultatami metody EOMCCSD wskazuje, że istnieje duża grupa stanów wzbudzonych, dla których bardzo dokładne rezultaty oferuje tylko metoda EOMCCSDT. Wykonane obliczenia angażowały do 160 orbitali molekularnych, co biorąc pod uwagę średnią jakość sprzętu komputerowego, na którym obliczenia były prowadzone, jest bardzo dobrym wynikiem dla tak dokładnej metody, jak EOMCCSDT. Użytkownicy dysponujący komputerami o lepszych parametrach będą mogli wykonywać bardzo dokładne obliczenia dla jeszcze większych układów. Dzięki moim obliczeniom można było dostarczyć nowe, dość dokładne dane teoretyczne, charakteryzujące stany wzbudzone układów otwartopowłokowych, dla których wartości eksperymentalne są niedostępne. Winienem wspomnieć, że w trakcie realizacji doktoratu podobny program został stworzony przez tandem Stanton - Gauss [122]. Wyniki opublikowane w pracy [123] są jednak pierwszymi w literaturze wartościami uzyskanymi metodą EOMCCSDT dla stanów otwartopowłokowych

An exploitation area of Szlachtowa ore as an element of the future Pieniny Geopark

One of the most interesting objects of the future Pieniny geopark would be the Jarmuta and Pałkowski stream adits. Traces of the mining heritage of an exploitation area of Szlachtowa ore are characterized by high scientific, historical, educational and cognitive values. The extraction of ore minerals which took place probably from XIV to XVIII century was connected with presence of polymetallic veins and hydrothermal processes around the andesite intrusions of the Eastern Polish part of the Pieniny Andesite Line (PAL). Historical mines exploited epithermal, poor gold- silver deposites. The land use within the Pieniny Geopark might contribute to reduction in tourist flows in the most popular and crowded parts of the Pieniny Mts

Using the charge-stabilization technique in the double ionization potential equation-of-motion calculations with dianion references

The charge-stabilization method is applied to double ionization potential equation-of-motion (EOM-DIP) calculations to stabilize unstable dianion reference functions. The auto-ionizing character of the dianionic reference states spoils the numeric performance of EOM-DIP limiting applications of this method. We demonstrate that reliable excitation energies can be computed by EOM-DIP using a stabilized resonance wave function instead of the lowest energy solution corresponding to the neutral + free electron(s) state of the system. The details of charge-stabilization procedure are discussed and illustrated by examples. The choice of optimal stabilizing Coulomb potential, which is strong enough to stabilize the dianion reference, yet, minimally perturbs the target states of the neutral, is the crux of the approach. Two algorithms of choosing optimal parameters of the stabilization potential are presented. One is based on the orbital energies, and another -on the basis set dependence of the total Hartree-Fock energy of the reference. Our benchmark calculations of the singlet-triplet energy gaps in several diradicals show a remarkable improvement of the EOM-DIP accuracy in problematic cases. Overall, the excitation energies in diradicals computed using the stabilized EOM-DIP are within 0.2 eV from the reference EOM spin-flip values

Extremal spacings between eigenphases of random unitary matrices and their tensor products

Extremal spacings between eigenvalues of random unitary matrices of size N pertaining to circular ensembles are investigated. Explicit probability distributions for the minimal spacing for various ensembles are derived for N = 4. We study ensembles of tensor product of k random unitary matrices of size n which describe independent evolution of a composite quantum system consisting of k subsystems. In the asymptotic case, as the total dimension N = n^k becomes large, the nearest neighbor distribution P(s) becomes Poissonian, but statistics of extreme spacings P(s_min) and P(s_max) reveal certain deviations from the Poissonian behavior

Functional and biochemical endothelial profiling in vivo in a murine model of endothelial dysfunction : comparison of effects of 1-methylnicotinamide and angiotensin-converting enzyme inhibitor

Although it is known that 1-methylnicotinamide (MNA) displays vasoprotective activity in mice, as yet the effect of MNA on endothelial function has not been demonstrated in vivo. Here, using magnetic resonance imaging (MRI) we profile the effects of MNA on endothelial phenotype in mice with atherosclerosis (ApoE/LDLR(-/-)) in vivo, in comparison to angiotensin (Ang) -converting enzyme (ACE) inhibitor (perindopril), with known vasoprotective activity. On a biochemical level, we analyzed whether MNA- or perindopril-induced improvement in endothelial function results in changes in ACE/Ang II-ACE2/Ang-(1–7) balance, and L-arginine/asymmetric dimethylarginine (ADMA) ratio. Endothelial function and permeability were evaluated in the brachiocephalic artery (BCA) in 4-month-old ApoE/LDLR(-/-) mice that were non-treated or treated for 1 month or 2 months with either MNA (100 mg/kg/day) or perindopril (10 mg/kg/day). The 3D IntraGate(®)FLASH sequence was used for evaluation of BCA volume changes following acetylcholine (Ach) administration, and for relaxation time (T(1)) mapping around BCA to assess endothelial permeability using an intravascular contrast agent. Activity of ACE/Ang II and ACE2/Ang-(1–7) pathways as well as metabolites of L-arginine/ADMA pathway were measured using liquid chromatography/mass spectrometry-based methods. In non-treated 6-month-old ApoE/LDLR(-/-) mice, Ach induced a vasoconstriction in BCA that amounted to –7.2%. 2-month treatment with either MNA or perindopril resulted in the reversal of impaired Ach-induced response to vasodilatation (4.5 and 5.5%, respectively) and a decrease in endothelial permeability (by about 60% for MNA-, as well as perindopril-treated mice). Improvement of endothelial function by MNA and perindopril was in both cases associated with the activation of ACE2/Ang-(1–7) and the inhibition of ACE/Ang II axes as evidenced by an approximately twofold increase in Ang-(1–9) and Ang-(1–7) and a proportional decrease in Ang II and its active metabolites. Finally, MNA and perindopril treatment resulted in an increase in L-arginine/ADMA ratio by 107% (MNA) and 140% (perindopril), as compared to non-treated mice. Functional and biochemical endothelial profiling in ApoE/LDLR(-/-) mice in vivo revealed that 2-month treatment with MNA (100 mg/kg/day) displayed a similar profile of vasoprotective effect as 2-month treatment with perindopril (10 mg/kg/day): i.e., the improvement in endothelial function that was associated with the beneficial changes in ACE/Ang II-ACE2/Ang (1–7) balance and in L-arginine/ADMA ratio in plasma

Heat shock factor 1 (Hsf1) cooperates with estrogen receptor α (erα) in the regulation of estrogen action in breast cancer cells

Heat shock factor 1 (HSF1), a key regulator of transcriptional responses to proteotoxic stress, was linked to estrogen (E2) signaling through estrogen receptor α (ERα). We found that an HSF1 deficiency may decrease ERα level, attenuate the mitogenic action of E2, counteract E2-stimulated cell scattering, and reduce adhesion to collagens and cell motility in ER-positive breast cancer cells. The stimulatory effect of E2 on the transcriptome is largely weaker in HSF1-deficient cells, in part due to the higher basal expression of E2-dependent genes, which correlates with the enhanced binding of unliganded ERα to chromatin in such cells. HSF1 and ERα can cooperate directly in E2-stimulated regulation of transcription, and HSF1 potentiates the action of ERα through a mechanism involving chromatin reorganization. Furthermore, HSF1 deficiency may increase the sensitivity to hormonal therapy (4-hydroxytamoxifen) or CDK4/6 inhibitors (palbociclib). Analyses of data from The Cancer Genome Atlas database indicate that HSF1 increases the transcriptome disparity in ER-positive breast cancer and can enhance the genomic action of ERα. Moreover, only in ER-positive cancers an elevated HSF1 level is associated with metastatic disease.publishedVersio

The absolute chronology of collective burials from the 2nd Millennium BC in East Central Europe

This article discusses the absolute chronology of collective burials of the Trzciniec Cultural Circle communities of the Middle Bronze Age in East Central Europe. Based on Bayesian modeling of 91 accelerator mass spectrometry radiocarbon (AMS 14C) dates from 18 cemeteries, the practice of collective burying of individuals was linked to a period of 400-640 (95.4%) years, between 1830–1690 (95.4%) and 1320-1160 (95.4%) BC. Collective burials in mounds with both cremation and inhumation rites were found earliest in the upland zone regardless of grave structure type (mounded or flat). Bayesian modeling of 14C determinations suggests that this practice was being transmitted generally from the southeast to the northwest direction. Bayesian modeling of the dates from the largest cemetery in Z· erniki Górne, Lesser Poland Upland, confirmed the duration of use of the necropolis as ca. 140–310 (95.4%) years. Further results show the partial contemporaneity of burials and allow formulation of a spatial and temporal development model of the necropolis. Based on the investigation, some graves were used over just a couple of years and others over nearly 200, with up to 30 individuals found in a single grave