14 research outputs found
Quantum information analysis of electronic states at different molecular structures
We have studied transition metal clusters from a quantum information theory
perspective using the density-matrix renormalization group (DMRG) method. We
demonstrate the competition between entanglement and interaction localization.
We also discuss the application of the configuration interaction based
dynamically extended active space procedure which significantly reduces the
effective system size and accelerates the speed of convergence for complicated
molecular electronic structures to a great extent. Our results indicate the
importance of taking entanglement among molecular orbitals into account in
order to devise an optimal orbital ordering and carry out efficient
calculations on transition metal clusters. We propose a recipe to perform DMRG
calculations in a black-box fashion and we point out the connections of our
work to other tensor network state approaches
Accurate ab initio spin densities
We present an approach for the calculation of spin density distributions for
molecules that require very large active spaces for a qualitatively correct
description of their electronic structure. Our approach is based on the
density-matrix renormalization group (DMRG) algorithm to calculate the spin
density matrix elements as basic quantity for the spatially resolved spin
density distribution. The spin density matrix elements are directly determined
from the second-quantized elementary operators optimized by the DMRG algorithm.
As an analytic convergence criterion for the spin density distribution, we
employ our recently developed sampling-reconstruction scheme [J. Chem. Phys.
2011, 134, 224101] to build an accurate complete-active-space
configuration-interaction (CASCI) wave function from the optimized matrix
product states. The spin density matrix elements can then also be determined as
an expectation value employing the reconstructed wave function expansion.
Furthermore, the explicit reconstruction of a CASCI-type wave function provides
insights into chemically interesting features of the molecule under study such
as the distribution of - and -electrons in terms of Slater
determinants, CI coefficients, and natural orbitals. The methodology is applied
to an iron nitrosyl complex which we have identified as a challenging system
for standard approaches [J. Chem. Theory Comput. 2011, 7, 2740].Comment: 37 pages, 13 figure
Tissue homeostasis: A tensile state
Mechanics play a significant role during tissue development. One of the key characteristics that underlies this mechanical role is the homeostatic pressure, which is the pressure stalling growth. In this work, we explore the possibility of a negative bulk homeostatic pressure by means of a mesoscale simulation approach and experimental data of several cell lines. We show how different cell properties change the bulk homeostatic pressure, which could explain the benefit of some observed morphological changes during cancer progression. Furthermore, we study the dependence of growth on pressure and estimate the bulk homeostatic pressure of five cell lines. Four out of five result in a bulk homeostatic pressure in the order of minus one or two kPa
Alpha-Carbonic Acid Revisited: Carbonic Acid Monomethyl Ester as a Solid and its Conformational Isomerism in the Gas Phase
In this work, earlier studies reporting alpha-H2CO3 are revised. The cryo-technique pioneered by Hage, Hallbrucker, and Mayer (HHM) is adapted to supposedly prepare carbonic acid from KHCO3. In methanolic solution, methylation of the salt is found, which upon acidification transforms to the monomethyl ester of carbonic acid (CAME, HO-CO-OCH3). Infrared spectroscopy data both of the solid at 210 K and of the evaporated molecules trapped and isolated in argon matrix at 10 K are presented. The interpretation of the observed bands on the basis of carbonic acid [as suggested originally by HHM in their publications from 1993-1997 and taken over by Winkel et al., J. Am. Chem. Soc. 2007 and Bernard et al., Angew. Chem. Int. Ed. 2011] is inferior compared with the interpretation on the basis of CAME. The assignment relies on isotope substitution experiments, including deuteration of the OH- and CH3- groups as well as C-12 and C-13 isotope exchange and on variation of the solvents in both preparation steps. The interpretation of the single molecule spectroscopy experiments is aided by a comprehensive calculation of high-level ab initio frequencies for gas-phase molecules and clusters in the harmonic approximation. This analysis provides evidence for the existence of not only single CAME molecules but also CAME dimers and water complexes in the argon matrix. Furthermore, different conformational CAME isomers are identified, where conformational isomerism is triggered in experiments through UV irradiation. In contrast to earlier studies, this analysis allows explanation of almost every single band of the complex spectra in the range between 4000 and 600 cm(-1)