2D-block geminals: A non 1-orthogonal and non 0-seniority model with reduced computational complexity.

We present a new geminal product wave function Ansatz where the geminals are not constrained to be strongly orthogonal or to be of seniority-zero. Instead, we introduce weaker orthogonality constraints between geminals that significantly lower the computational effort without sacrificing the indistinguishability of the electrons. That is to say, the electron pairs corresponding to the geminals are not fully distinguishable, and their product has yet to be antisymmetrized according to the Pauli principle to form a bona fide electronic wave function. Our geometrical constraints translate into simple equations involving the traces of products of our geminal matrices. In the simplest non-trivial model, a set of solutions is given by block-diagonal matrices where each block is 2 × 2 and consists of either a Pauli matrix or a normalized diagonal matrix multiplied by a complex parameter to be optimized. With this simplified Ansatz for geminals, the number of terms in the calculation of the matrix elements of quantum observables is considerably reduced. A proof of principle is reported and confirms that the Ansatz is more accurate than strongly orthogonal geminal products while remaining computationally affordable.

Orientational decoherence within molecules and emergence of the molecular shape.

The question of classicality is addressed in relation with the shape of the nuclear skeleton of molecular systems. As the most natural environment, the electrons of the molecule are considered as continuously monitoring agents for the nuclei. For this picture, an elementary formalism of decoherence theory is developed and numerical results are presented for few-particle systems. The numerical examples suggest that the electron-nucleus Coulomb interaction is sufficient for inducing a blurred shape with strong quantum coherences in compounds of the lightest elements, H2, D2, T2, and HeH+.

Theoretical Study of the Anisotropy Spectra of the Valine Zwitterion and Glyceraldehyde.

The electronic absorption (EA), circular dichroism (ECD), and anisotropy spectra of the l-valine zwitterion and d-glyceraldehyde are calculated by time-dependent density functional theory (TDDFT) with the M06-2X and B3LYP functionals. It is found that the absorption and ECD spectra from TDDFT/M06-2X agree well with experimental results measured from the amorphous film of l-valine. Moreover, the calculations reproduce all three major peaks observed in the experimental anisotropy spectra. For d-glyceraldehyde, the TDDFT/M06-2X calculations indicate that the excitation wavelengths of the first excited state of 32 stable conformers distribute from 288 to 322 nm, giving rise to two ECD peaks with opposite signs centered at 288 and 322 nm. The very weak absorption of the first excited state (S1) induces two high peaks in the anisotropy spectra of d-glyceraldehyde, which should be seen in future experimental studies.

Anharmonic vibrational spectroscopy of polycyclic aromatic hydrocarbons (PAHs).

While powerful techniques exist to accurately account for anharmonicity in vibrational molecular spectroscopy, they are computationally very expensive and cannot be routinely employed for large species and/or at non-zero vibrational temperatures. Motivated by the study of Polycyclic Aromatic Hydrocarbon (PAH) emission in space, we developed a new code, which takes into account all modes and can describe all infrared transitions including bands becoming active due to resonances as well as overtone, combination, and difference bands. In this article, we describe the methodology that was implemented and discuss how the main difficulties were overcome, so as to keep the problem tractable. Benchmarking with high-level calculations was performed on a small molecule. We carried out specific convergence tests on two prototypical PAHs, pyrene (C16H10) and coronene (C24H12), aiming at optimising tunable parameters to achieve both acceptable accuracy and computational costs for this class of molecules. We then report the results obtained at 0 K for pyrene and coronene, comparing the calculated spectra with available experimental data. The theoretical band positions were found to be significantly improved compared to harmonic density functional theory calculations. The band intensities are in reasonable agreement with experiments, the main limitation being the accuracy of the underlying calculations of the quartic force field. This is a first step toward calculating moderately high-temperature spectra of PAHs and other similarly rigid molecules using Monte Carlo sampling.

Anisotropy-Guided Enantiomeric Enhancement in Alanine Using Far-UV Circularly Polarized Light.

All life on Earth is characterized by its asymmetry - both the genetic material and proteins are composed of homochiral monomers. Understanding how this molecular asymmetry initially arose is a key question related to the origins of life. Cometary ice simulations, L-enantiomeric enriched amino acids in meteorites and the detection of circularly polarized electromagnetic radiation in star-forming regions point to a possible interstellar/protostellar generation of stereochemical asymmetry. Based upon our recently recorded anisotropy spectra g(λ) of amino acids in the vacuum-UV range, we subjected amorphous films of racemic (13)C-alanine to far-UV circularly polarized synchrotron radiation to probe the asymmetric photon-molecule interaction under interstellar conditions. Optical purities of up to 4% were reached, which correlate with our theoretical predictions. Importantly, we show that chiral symmetry breaking using circularly polarized light is dependent on both the helicity and the wavelength of incident light. In order to predict such stereocontrol, time-dependent density functional theory was used to calculate anisotropy spectra. The calculated anisotropy spectra show good agreement with the experimental ones. The European Space Agency's Rosetta mission, which successfully landed Philae on comet 67P/Churyumov-Gerasimenko on 12 November 2014, will investigate the configuration of chiral compounds and thereby obtain data that are to be interpreted in the context of the results presented here.

Photonenergy-controlled symmetry breaking with circularly polarized light.

Circularly polarized light (CPL) is known to be a true chiral entity capable of generating absolute molecular asymmetry. However, the degree of inducible optical activity depends on the λ of the incident CPL. Exposure of amorphous films of rac-alanine to tunable CPL led to enantiomeric excesses (ee) which not only follow the helicity but also the energy of driving electromagnetic radiation. Postirradiation analyses using enantioselective multidimensional GC revealed energy-controlled ee values of up to 4.2 %, which correlate with theoretical predictions based on newly recorded anisotropy spectra g(λ). The tunability of asymmetric photochemical induction implies that both magnitude and sign can be fully controlled by CPL. Such stereocontrol provides novel insights into the wavelength and polarization dependence of asymmetric photochemical reactions and are highly relevant for absolute asymmetric molecular synthesis and for understanding the origins of homochirality in living matter.

Contributions of the electronic spin and orbital current to the CoCl4(2-) magnetic field probed in polarised neutron diffraction experiments.

Polarised neutron diffraction experiments conducted at 4.2 K on Cs(3)CoCl(5) crystals have been analysed by using a four-dimensional model Hilbert space made of ab initio n-electron wave functions of the CoCl(4)(2-) molecular ion. Two spin-orbit mixing coefficients and several configuration interaction coefficients have been optimized by fitting calculated magnetic structure factors to experimental ones, to obtain the best ensemble density operator that is representable in the model space. A goodness of fit, χ(2), less then 1 has been obtained for the first time for the two experimental data sets available. In the present article, the optimized density operators are used to calculate the magnetic field densities that are the genuine observables probed in neutron diffraction experiments. Density maps of such observables are presented for the first time and numerical details are provided. The respective contributions of spin density and orbital current to the magnetic field density are analyzed.

A comparison of two methods for selecting vibrational configuration interaction spaces on a heptatomic system: ethylene oxide.

Two recently developed methods for solving the molecular vibrational Schrodinger equation, namely, the parallel vibrational multiple window configuration interaction and the vibrational mean field configuration interaction, are presented and compared on the same potential energy surface of ethylene oxide, c-C(2)H(4)O. It is demonstrated on this heptatomic system with strong resonances that both approaches converge towards the same fundamental frequencies. This confirms their ability to tackle the vibrational problem of large molecules for which full configuration interaction calculations are not tractable.

The electronic mean-field configuration interaction method. I. Theory and integral formulas.

In this article, we introduce a new method for solving the electronic Schrodinger equation. This new method follows the same idea followed by the mean-field configuration interaction method already developed for molecular vibrations; i.e., groups of electronic degrees of freedom are contracted together in the mean field of the other degrees. If the same partition of electronic degrees of freedom is iterated, a self-consistent field method is obtained. Making coarser partitions (i.e., including more degrees in the same groups) and discarding the high energy states, the full configuration interaction limit can be approached. In contrast with the usual group function theory, no strong orthogonality condition is enforced. We have made use of a generalized version of the fundamental formula defining a Hopf algebra structure to derive Hamiltonian and overlap matrix element expressions which respect the group structure of the wave function as well as its fermionic symmetry. These expressions are amenable to a recursive computation.