High resolution spectroscopy of methyltrioxorhenium: towards the observation of parity violation in chiral molecules

Originating from the weak interaction, parity violation in chiral molecules has been considered as a possible origin of biohomochirality. We have proposed the observation of molecular parity violation using the two-photon Ramsey fringes technique on a supersonic beam. As a first step in this direction, a detailed spectroscopic study of methyltrioxorhenium (MTO) has been undertaken. It is an ideal test molecule as the achiral parent molecule of chiral candidates for a parity violation experiment. For the (187)Re MTO isotopologue, a combined analysis of Fourier transform microwave and infrared spectra as well as ultra-high resolution CO(2) laser absorption spectra enabled the assignment of 28 rotational lines and 71 rovibrational lines, some of them with a resolved hyperfine structure. A set of spectroscopic parameters in the ground and first excited state, including hyperfine structure constants, was obtained for the ν(as) antisymmetric Re=O stretching mode of this molecule. This result validates the experimental approach to be followed once a chiral derivative of MTO is synthesized, and shows the benefit of the combination of several spectroscopic techniques in different spectral regions, with different set-ups and resolutions. The first high resolution spectra of jet-cooled MTO, obtained on a set-up being developed for the observation of molecular parity violation, are shown, which constitutes a major step towards the targeted objective.     

Quantum stochastic resonance in parity violating chiral molecules

In order to explore parity violating effects in chiral molecules, of interest in some models of evolution towards homochirality, quantum stochastic resonance (QSR) is studied for the population difference between the two enantiomers of a chiral molecule (hence for the optical activity of the sample), under low viscous friction and in the deep quantum regime. The molecule is described by a two-state model in an asymmetric double well potential where the asymmetry is given by the known predicted parity violating energy difference (PVED) between enantiomers. In the linear response to an external driving field that lowers and rises alternatively each one of the minima of the well, a signal of QSR is predicted only in the case that the PVED is different from zero, the resonance condition being independent on tunneling between the two enantiomers. It is shown that, at resonance, the fluctuations of the first order contribution to the internal energy are zero. Due to the small value of the PVED, the resonance would occur in the ultracold regime. Some proposals concerning the external driving field are suggested.     

Recent experimental and theoretical developments towards the observation of parity violation (PV) effects in molecules by spectroscopy

Parity violation (PV) at the molecular level is known to be responsible for a tiny energy difference between the two enantiomers of a chiral molecule. This parity violation energy difference (PVED) has not yet been detected by experiment. In the last few years, the search for PV effects in molecules has made important steps ahead for several reasons. On one hand, very accurate infra-red spectroscopy measurements were performed by metrologists on bromochlorofluoromethane (CHFClBr) with a 10 Hz accuracy, which so far is the most precise. On the other hand, relativistic calculations were used for the evaluation of DeltaE(PV) allowing for a screening of favorable molecules for future measurements. The synthesis of such chiral molecules with high parity violation effects is currently being investigated. In memory of Professor Jean-Bernard Robert.     

Coordination properties of axially unfixed chiral dipyridine ligands towards metal and ammonium ions

New chiral dipyridine ligands with an axially unfixed 1,1′-biphenyl bridge were prepared via homocoupling of bromophenyl pyridines. The conformeric ratios of the free ligands in solution and their coordination properties towards metal ions were studied by NMR spectroscopy. X-Ray crystallography of the silver(I) and copper(I) complexes showed 1:1 metal to ligand complexes and S planar chirality. Interestingly, the biphenyl ligands show a 1:2 stepwise binding towards most ammonium ions tested with strong fluorescence enhancement, but a selectively 1:1 binding towards l-ornithine methyl ester hydrochloride with no fluorescence enhancement.     

Molecular diffusion in liquid crystals and chiral discrimination. I. Theory

The possibility of using cholesteric phases for discriminating enantiomers of a chiral solute on the basis of their different transport properties, motivates the investigation of the translational diffusion by taking fully into account the roto-translational coupling. In this article a detailed theoretical analysis is presented for the transport properties evaluated according to the asymptotic limit of the mean-squared displacement. A general relation is derived for the transport coefficients, having as main ingredients the mean-field potential due to the mesophase, and the diffusion tensor with its purely translational and rotational components, and with the blocks describing the roto-translational coupling. The application of the theory to nematic phases shows that the roto-translational coupling generates a dynamical contribution reducing the transport coefficients evaluated by taking into account only the translational diffusion components in the center of diffusion. The theory is also specialized to a cholesteric phase with a given helical pitch for the director arrangement, in a form which is suitable for calculations of model systems of chiral solutes to be presented in a forthcoming paper.     

Vibrational spectra of 1,3-dideuterioallene and normal mode calculations for allene

Infrared and Raman spectra of 1,3-d₂-allene were measured and fundamental frequencies were assigned. The frequencies were used with previously published data for the d₀, d₄, d₁ and 1,1,-d₂ isotopomers of allene in force field calculations. A new ab initio quantum mechanical force field calculated at the 6-31G** level was scaled to fit the anharmonic fundamental frequencies and used to provide some of the interaction constants for a second, conventionally refined force field.     

A self-consistent molecular field theory for aggregates of neutral molecules. I

A self-consistent theory is presented for aggregates of neutral molecules. According to the LCAO Hartree-Fock formalism a set of effective Hartree-Fock equations for molecules in the aggregate is derived. The molecular orbitals of each molecule are to be determined from the effective H-F equation for the molecule in which the interactions between the molecule and the surrounding ones are included as an intermolecular interaction field (molecular field). A self-consistent treatment leads to the molecular orbitals which are self-consistent with the molecular field. By this method, then-molecule problem becomesn times of one-molecule problem.     

A generalized formula for the energies of alternant molecular orbitals. I. Homonuclear molecules

Using the method of alternant molecular orbitals (AMO ) it is shown that the energies of AMO 's (E_k), for any alternant homonuclear molecule having a singlet ground state, are connected with the energies of the MO 's (e_k) obtained by the conventional Hartree–Fock (HF ) method by the formula \documentclass{article}\pagestyle{empty}\begin{document}$ E_{k\alpha (\beta )} = \pm \sqrt {\Delta ^2 + e_k ^2 } $\end{document}, where Δ is the correlation correction. The formula is applicable in the semiempirical LCAO form used in the Pariser–Parr–Pople theory, by Hubbard's approximation of γ integrals.     

The preparation of 1,3-bis(trimethylsilyl)allene and the observation of the enantiomers using olefin complexing chiral shift reagents

1,3-Bis(trimethylsilyl)allene was prepared.     

Bis(heterocumulenes) derived from the 1,4-diphenyl-1,3-butadiyne framework. Synthesis of three new classes of axially chiral biheteroaryls

Bis(ketenimines) and bis(carbodiimides) derived from 1,4-bis(2-aminophenyl)-1,3-butadiynes via two independent biradical cyclizations provided, respectively, axially chiral bis(benzocarbazoles) and bis(quinindolines). Mixed biheteroaryls, consisting of benzocarbazole and quinindoline units, have been also prepared by a slightly modified strategy.     

Analysis of molecular orbital wave functions in terms of valence bond functions for molecular fragments. I. Theory

A method of expansion of molecular orbital wave functions into valence bond (VB ) functions is extended to molecular fragments. The wave function is projected onto a basis of mixed determinants, involving molecular orbitals as well as fragment atomic orbitals, and is further expressed as a linear combination of VB functions, characteristic of structural formulas of the fragment but whose remaining bonds are frozen. Structural weights for the fragment are deduced from this expression. Delocalized molecular orbitals are used as a startpoint, as they are after an ordinary SCF calculation. Wave functions of medium-sized molecules may be analyzed with reasonable storage requirements in a computer.     

Theory and algorithms for the excited states of large molecules and molecular aggregates

This project aims to attack the frontiers of electronic structure calculations on the excited states of large molecules and molecular aggregates by developing novel theoretical and computational methods. The methodology development is especially based on the time-dependent density functional theory (TDDFT) and valence bond (VB) theory, and is expected to be computationally effective and accurate as well. Research works on the following related subjects will be performed: (1) The analytical energy-derivative approaches for electronically excited state within TDDFT will be developed to reduce bypass the computational costs in the calculation of molecular excited-state properties. (2) The ab initio methods for electronically excited state based on VB theory and hybrid TDDFT-VB method will be developed to overcome the limitations of current TDDFT in simulating photophysics and photochemistry. (3) For larger aggregates, neither ab initio methods nor TDDFT is applicable. We intend to build the effective model Hamiltonian by developing novel theoretical and computational methods to calculate the involved microscopic physical parameters from the first-principles methods. The constructed effective Hamiltonian is then used to describe the excitonic states and excitonic dynamics of the natural or artificial photosynthesized systems, organic or inorganic photovoltaic cell. (4) The condensed phase environment is taken into account by combining the developed theories and algorithms based on TDDFT and VB with the polarizable continuum solvent models (PCM), molecular mechanism (MM), classical electrodynamics (ED) or molecular dynamics (MD) theory. (5) Highly efficient software packages will be designed and developed.     

An Hg2+-gated chiral molecular switch created by using binaphthalene molecules with two anthracene units and two 1,3-dithiole-2-thione (1,3-dithiole-2-one) units

By integrating the features of anthracene, 1,3-dithiole-2-thione, and binaphthalene units, (S)-1 and its analogue (S)-2, which contains two 1,3-dithiole-2-one units instead of 1,3-dithiole-2-thione, were studied for creating a new molecular regulation system and building a gated chiral molecular switch. The results show that the photodimerization is controlled by the remote functional-group transformation of C=S into C=O, thus providing an elegant example of molecular regulation. The photodimerization of two anthracene units induces circular dichroism (CD) spectral variation. Overall, the CD spectrum can be remotely modulated by Hg2+ in (S)-1, which leads to an Hg2+-gated chiral molecular switch.     

Spectroscopic investigation of local molecular dynamics in liquid crystals I. Small molecules

The dynamics of liquid crystal systems, consisting of either small molecules or polymer chains with main-chain or side-chain mesogenic groups, can be investigated using the same spectroscopic techniques which are applied to isotropic systems. This article briefly reviews ¹H, ¹³C and ²H N.M.R. and E.S.R. spectroscopy as well as dielectric relaxation. The particular features related to the oriented nature of the liquid crystal phases are developed. Typical examples of studies performed on small-molecule liquid crystals using these various spectroscopic techniques are described.     

Orientation and molecular dynamics in uniaxial polymers. I. Theory of fluorescence polarization

A theory of polarized fluorescence is developed for uniaxial physical systems in which micro-Brownian motion is not negligible. All experimental information is shown to reduce, with reasonable assumptions, to four quantities characterizing molecular orientation and reorientational molecular mobility. The geometrical properties of the mobility in uniaxial systems are studied and methods are given for correcting for the effects of the birefringence and for a possible delocalization of the fluorescence transition moments.     

First enantiopure calix[6]aza-cryptand: synthesis and chiral recognition properties towards neutral molecules

The synthesis of the first enantiopure calix[6]aza-cryptand was achieved in five steps from the known 1,3,5-tris-O-methylated calix[6]arene. A ¹H NMR spectroscopic study has shown that the chiral tren cap constrains the calixarene core in a straight cone conformation ideal for host–guest chemistry applications. As a result, the tetra-protonated derivative displays remarkable host properties towards polar neutral molecules and enantioselective recognition processes have been evidenced with chiral guests.     

Space-time contours to treat intense field-dressed molecular states. I. Theory

A molecular system exposed to an intense external field is considered. The strength of the field is measured by the number L of electronic states that become populated during this process. In the present article the authors discuss a rigorous way, based on the recently introduced space-time contours [R. Baer, et al., J. Chem. Phys. 119, 6998 (2003)], to form N coupled Schrodinger equations where N相似文献   

Full-dimensional quantum calculations of vibrational spectra of six-atom molecules. I. Theory and numerical results

Two quantum mechanical Hamiltonians have been derived in orthogonal polyspherical coordinates, which can be formed by Jacobi and/or Radau vectors etc., for the study of the vibrational spectra of six-atom molecules. The Hamiltonians are expressed in an explicit Hermitian form in the spatial representation. Their matrix representations are described in both full discrete variable representation (DVR) and mixed DVR/nondirect product finite basis representation (FBR) bases. The two-layer Lanczos iteration algorithm [H.-G. Yu, J. Chem. Phys. 117, 8190 (2002)] is employed to solve the eigenvalue problem of the system. A strategy regarding how to carry out the Hamiltonian-vector products for a high-dimensional problem is discussed. By exploiting the inversion symmetry of molecules, a unitary sequential 1D matrix-vector multiplication algorithm is proposed to perform the action of the Hamiltonian on the wavefunction in a symmetrically adapted DVR or FBR basis in the azimuthal angular variables. An application to the vibrational energy levels of the molecular hydrogen trimer (H2)3 in full dimension (12D) is presented. Results show that the rigid-H2 approximation can underestimate the binding energy of the trimer by 27%. Finally, it is demonstrated that the two-layer Lanczos algorithm is also capable of computing the eigenvectors of the system with minor effort.     

脱氧胆酸手性分子钳的微波合成及其对中性分子的识别性能研究

在微波辐射条件下,以脱氧胆酸甲酯为间隔基,高产率合成了5个脱氧胆酸手性分子钳人工受体,其结构经IR,1HNMR,MS及元素分析确证。用差紫外光谱法测定了其对中性分子的识别性能。实验结果表明,这类分子钳人工受体对所考察的客体分子有良好的识别作用,主客体间形成1∶1型主客体配合物,受体5d对苯胺的结合常数高达14171.39 M-1。