Understanding the mechanism stabilizing intermediate spin states in Fe(II)-Porphyrin

Spin fluctuations in Fe(II)-porphyrins are at the heart of heme-proteins functionality. Despite significant progress in porphyrin chemistry, the mechanisms that rule spin state stabilisation remain elusive. Here, it is demonstrated by using multiconfigurational quantum chemical approaches, including the novel Stochastic-CASSCF method, that electron delocalization between the metal centre and the pi system of the macrocycle differentially stabilises the triplet spin states over the quintet. This delocalisation takes place via charge-transfer excitations, involving the out-of-plane iron d orbitals, key linking orbitals between metal and macrocycle. Through a correlated breathing mechanism, the 3d electrons can make transitions towards the pi orbitals of the macrocycle. This guarantees a strong coupling between the on-site radial correlation on the metal and electron delocalization. Opposite-spin 3d electrons of the triplet can effectively reduce electron repulsion in this manner. Constraining the out-of-plane orbitals from breathing hinders delocalization and reverses the spin ordering. Our results find a qualitative analogue in Kekul\'e resonance structures involving also the metal centre

On groups with the same character degrees as almost simple groups with socle the Mathieu groups

Let $G$ be a finite group and $cd(G)$ denote the set of complex irreducible character degrees of $G$. In this paper, we prove that if $G$ is a finite group and $H$ is an almost simple group whose socle is Mathieu group such that $cd(G) =cd(H)$, then there exists an Abelian subgroup $A$ of $G$ such that $G/A$ is isomorphic to $H$. This study is heading towards the study of an extension of Huppert's conjecture (2000) for almost simple groups.Comment: arXiv admin note: text overlap with arXiv:1108.0010 by other author

Can Turkey really be a political model for its region?

From the outset of the ‘Arab Spring’, Turkey has pursued an active foreign policy and supported a number of recent popular uprisings throughout the Arab world. Having appeared on Arab TV channels such as Al Jazeera and Al Arabiya to express Turkish support of political opposition in revolutionary Arab countries, Turkey’s Foreign Minister, Ahmet Davutoglu, is now a familiar and popular figure in the Arab world. The Turkish Prime Minister, Recep Tayyip Erdogan, conducted an ‘Arab Spring Tour’, where he visited post-uprising Tunisia, Egypt and Libya. In his visit to the latter, Erdogan was greeted at the airport by chairman of Libya’s new National Transitional Council, Mustafa Abdul-Jalil. He has even been compared by some to the late Gamal Abdel Nasser, whose pan Arab propaganda, amongst other factors, made him a regional hero in the 1950s

Non-linear biases, stochastically-sampled effective Hamiltonians and spectral functions in quantum Monte Carlo methods

In this article we study examples of systematic biases that can occur in quantum Monte Carlo methods due to the accumulation of non-linear expectation values, and approaches by which these errors can be corrected. We begin with a study of the Krylov-projected FCIQMC (KP-FCIQMC) approach, which was recently introduced to allow efficient, stochastic calculation of dynamical properties. This requires the solution of a sampled effective Hamiltonian, resulting in a non-linear operation on these stochastic variables. We investigate the probability distribution of this eigenvalue problem to study both stochastic errors and systematic biases in the approach, and demonstrate that such errors can be significantly corrected by moving to a more appropriate basis. This is lastly expanded to include consideration of the correlation function QMC approach of Ceperley and Bernu, showing how such an approach can be taken in the FCIQMC framework.Comment: 12 pages, 7 figure

A Full Configuration Interaction Perspective on the Homogeneous Electron Gas

Highly accurate results for the homogeneous electron gas (HEG) have only been achieved to date within a diffusion Monte Carlo (DMC) framework. Here, we introduce a newly developed stochastic technique, Full Configuration Interaction Quantum Monte Carlo (FCIQMC), which samples the exact wavefunction expanded in plane wave Slater determinants. Despite the introduction of a basis set incompleteness error, we obtain a finite-basis energy which is significantly, and variationally lower than any previously published work for the 54-electron HEG at $r_s$ = 0.5 a.u., in a Hilbert space of $10^{108}$ Slater determinants. At this value of $r_s$, as well as of 1.0 a.u., we remove the remaining basis set incompleteness error by extrapolation, yielding results comparable or better than state-of-the-art DMC backflow energies. In doing so, we demonstrate that it is possible to yield highly accurate results with the FCIQMC method in sizable periodic systems.Comment: 4-page lette