Predicting the FCI Energy of Large Systems to Chemical Accuracy from Restricted Active Space Density Matrix Renormalization Group Calculations.

We theoretically derive and validate with large scale simulations a remarkably accurate power law scaling of errors for the restricted active space density matrix renormalization group (DMRG-RAS) method [J. Phys. Chem.

Toward Large-Scale Restricted Active Space Calculations Inspired by the Schmidt Decomposition.

We present an alternative, memory-efficient, Schmidt decomposition-based description of the inherently bipartite restricted active space (RAS) scheme, which can be implemented effortlessly within the density matrix renormalization group (DMRG) method via the dynamically extended active space procedure. Benchmark calculations are compared against state-of-the-art results of C and Cr, which are notorious for their multireference character. Our results for ground and excited states together with spectroscopic constants demonstrate that the proposed novel approach, dubbed as DMRG-RAS, which is variational and free of uncontrolled method errors, has the potential to outperfom conventional methods for strongly correlated molecules.

Sensitivity of coupled cluster electronic properties on the reference determinant: Can Kohn-Sham orbitals be more beneficial than Hartree-Fock orbitals?

Coupled cluster calculations are traditionally performed over Hartree-Fock reference orbitals (HF-CC methodology). However, in the literature it has been repeatedly raised whether the use of a Kohn-Sham reference (KS-CC methodology) might result in improved performance relative to HF-CC. In the present study, we re-examine the relation of HF-CC and KS-CC methods by comparing the results of widely applied truncated CC calculations (CCSD, CCSD(T), CCSDT) to the limit of full configuration interaction (FCI), which serves as an undebatable reference point of accuracy.

DMRG on Top of Plane-Wave Kohn-Sham Orbitals: A Case Study of Defected Boron Nitride.

In this paper, we analyze the numerical aspects of the inherent multireference density matrix renormalization group (DMRG) calculations on top of the periodic Kohn-Sham density functional theory using the complete active space approach. The potential of the framework is illustrated by studying hexagonal boron nitride nanoflakes embedding a charged single boron vacancy point defect by revealing a vertical energy spectrum with a prominent multireference character. We investigate the consistency of the DMRG energy spectrum from the perspective of sample size, basis size, and active space selection protocol.

Quantum information-based analysis of electron-deficient bonds.

Recently, the correlation theory of the chemical bond was developed, which applies concepts of quantum information theory for the characterization of chemical bonds, based on the multiorbital correlations within the molecule. Here, for the first time, we extend the use of this mathematical toolbox for the description of electron-deficient bonds. We start by verifying the theory on the textbook example of a molecule with three-center two-electron bonds, namely, diborane(6).

The correlation theory of the chemical bond.

The quantum mechanical description of the chemical bond is generally given in terms of delocalized bonding orbitals, or, alternatively, in terms of correlations of occupations of localised orbitals. However, in the latter case, multiorbital correlations were treated only in terms of two-orbital correlations, although the structure of multiorbital correlations is far richer; and, in the case of bonds established by more than two electrons, multiorbital correlations represent a more natural point of view. Here, for the first time, we introduce the true multiorbital correlation theory, consisting of a framework for handling the structure of multiorbital correlations, a toolbox of true multiorbital correlation measures, and the formulation of the multiorbital correlation clustering, together with an algorithm for obtaining that.

Hückel-Hubbard-Ohno modeling of π-bonds in ethene and ethyne with application to trans-polyacetylene.

Quantum chemistry calculations provide the potential energy between two carbon atoms in ethane (H3C-CH3), ethene (H2C[double bond, length as m-dash]CH2), and ethyne (HC[triple bond, length as m-dash]CH) as a function of the atomic distance. Based on the energy function for the σ-bond in ethane, Vσ(r), we use the Hückel model with Hubbard-Ohno interaction for the π electrons to describe the energies Vσπ(r) and Vσππ(r) for the σπ double bond in ethene and the σππ triple bond in ethyne, respectively. The fit of the force functions shows that the electron transfer matrix element and the Peierls coupling can be estimated with some precision whereas the Hubbard-Ohno parameters are insignificant at the distances under consideration.

On the calculation of complete dissociation curves of closed-shell pseudo-onedimensional systems via the complete active space method of increments.

The method of increments (MoI) has been employed using the complete active space formalism in order to calculate the dissociation curve of beryllium ring-shaped clusters Be(n) of different sizes. Benchmarks obtained through different quantum chemical methods including the ab initio density matrix renormalization group were used to verify the validity of the MoI truncation which showed a reliable behavior for the whole dissociation curve. Moreover we investigated the size dependence of the correlation energy at different interatomic distances in order to extrapolate the values for the periodic chain and to discuss the transition from a metal-like to an insulator-like behavior of the wave function through quantum chemical considerations.

Orbital Entanglement in Bond-Formation Processes.

The accurate calculation of the (differential) correlation energy is central to the quantum chemical description of bond-formation and bond-dissociation processes. In order to estimate the quality of single- and multireference approaches for this purpose, various diagnostic tools have been developed. In this work, we elaborate on our previous observation [J.

Inducibility of the hepatic microsomal monooxygenase system experimentally reduced to a minimum amount/activity. Effect of hypophysectomy, partial hepatectomy and phenobarbital/toluene treatment on the hepatic polysubstrate monooxygenase system in rats.

Sham-operated, hypophysectomized, partially hepatectomized and hypophysectomized + partially hepatectomized groups of CFY rats were treated with phenobarbital (40 mg/kg/day) per os or physiological saline once a day, or toluene-vapour (inhalation: 4,000 mg/m3, 8 h/day), for 3 days. The polysubstrate monooxygenase (PSMO) system of the liver was induced by phenobarbital after all kinds of surgical interventions. Inducibility of the enzyme system was the highest in the group with combined hypophysectomy + partial hepatectomy and decreased in order in the groups with partial hepatectomy, hypophysectomy and sham-operation.

Combined embryotoxic action of toluene, a widely used industrial chemical, and acetylsalicylic acid (aspirin).

CFY rats were exposed to inhalation of fresh air at days 10-13 of gestation; at day 12 the dams were given 0, 125, 250, 500, or 1,000 mg/kg acetylsalicylic acid (ASA) by gavage. During the same period of gestation (days 10-13) further groups of rats were exposed to toluene at 1,000, 2,000, and 3,600 mg/m3 atmospheric concentration and were given 250 mg/kg ASA by gavage; two subgroups of animals treated with 250 mg/kg ASA in combination with 3,600 mg/m3 toluene inhalation were given 0, 2.5, or 5 gm/kg glycine 2 hours before the ASA dose.

Comparative study on the acute effects of benzene, toluene and m-xylene in the rat.

Solvents were tested for their influence on motivational state, as well as for their sedative effects, after intraperitoneal administration. The following tests were used: open field (exploratory activity, locomotion), activity wheel (running activity), tube test and tilted plane (muscle weakness, incoordination). The agents proved to be similar in causing muscle weakness and ataxia already at low dose levels.

[Correlation between the fetotoxic effect of benzol inhalation in CFY rats and benzol concentration in the inhaled gas].

CFY rats from the 7th to the 14th days of pregnancy were given benzole to inhale during 24 hours a day in doses 150, 450, 1500 or 3000 mg/m3 (50, 150, 500 or 1000 ppm). It was established that benzole has no teratogenous effect in rats. Frequency of the obvious malformations of the scelet and soft tissues has not increase at any doses given.

Concentration dependence of the embryotoxic effects of benzene inhalation in CFY rats.

CFY rats were exposed to continuous benzene inhalation 24 h/day from day 7 to day 14 of gestation at 150, 450, 1500, or 3000 mg/m3 (50, 150, 500, or 1000 ppm) atmospheric concentrations. None of the benzene concentrations used proved to be teratogenic. There was no increase in the incidence of external, visceral, or skeletal malformations.