Separating Para and Ortho Water

Water exists as two nuclear‐spin isomers, para and ortho, determined by the overall spin of its two hydrogen nuclei. For isolated water molecules, the conversion between these isomers is forbidden and they act as different molecular species. Yet, these species are not readily separated, and no pure para sample has been produced. Accordingly, little is known about their specific physical and chemical properties, conversion mechanisms, or interactions. The production of isolated samples of both spin isomers is demonstrated in pure beams of para and ortho water in their respective absolute ground state. These single‐quantum‐state samples are ideal targets for unraveling spin‐conversion mechanisms, for precision spectroscopy and fundamental symmetry‐breaking studies, and for spin‐enhanced applications, for example laboratory astrophysics and astrochemistry or hypersensitized NMR experiments.     

Nuclear spin selective laser control of rotational and torsional dynamics

We explore the possibility of controlling rotational-torsional dynamics of non-rigid molecules with strong, non-resonant laser pulses and demonstrate that transient, laser-induced torsional alignment depends on the nuclear spin of the molecule. Consequently, nuclear spin isomers can be manipulated selectively by a sequence of time-delayed laser pulses. We show that two pulses with different polarization directions can induce either overall rotation or internal torsion, depending on the nuclear spin. Nuclear spin selective control of the angular momentum distribution may open new ways to separate and explore nuclear spin isomers of polyatomic molecules.     

Nuclear spin selection rules for reactive collision systems by the spin-modification probability method

The spin-modification probability (SMP) method, which provides fundamental and detailed quantitative information on the nuclear spin selection rules, is discussed more systematically and generalized for reactive collision systems involving more than one configuration of reactant and product molecules, explicitly taking account of the conservation of the overall nuclear spin symmetry as well as the conservation of the total nuclear spin angular momentum, under the assumption of no nuclear hyperfine interaction. The values of SMP once calculated can be used for any system of identical nuclei of any spin as long as the system has the corresponding nuclear spin symmetry. The values of SMP calculated for simple systems can also be used for more complex systems containing several kinds of identical nuclei or various isotopomers. The generalized formulation of statistical scattering theory which can easily represent various rearrangement mechanisms is also presented.     

Bonding in benzene methylene isomers: Modern VB study using spin-coupled theory

The electronic structure of the benzene methylene isomers fulvene, dimethylenecyclobutene, and trimethylenecyclopropene is studied using spin-coupled theory. It is shown that the three isomers all possess three noninteracting π-bonds and very low resonance energies. This is to be contrasted with benzene, where the symmetric coupling of the π-electron spins around the ring provides a considerable larger resonance energy. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 319–327, 1999     

咪唑氧自由基分子NLO性质的密度泛函理论研究

采用密度泛函理论(DFT) UB3LYP方法, 在6-31g(d)水平上对2,2’-(1,2-乙炔基-4,1-亚苯基)双[4,4’,5,5’-四氢]咪唑氧自由基分子及其异构体的自旋耦合性质进行分析, 并结合有限场(FF)方法计算它们的非线性光学(NLO)系数, 以探讨咪唑氧环在共轭链不同位置时体系的自旋耦合规律和NLO系数. 结果表明, 所有体系基态自旋符合自旋极化规则, 它们的极化率随自旋多重度的增加而减小; 一阶超极化率因受分子对称性影响, 对称性不同其一阶超极化率的变化也不同; 二阶超极化率呈现随着自旋多重度的增加而增加的趋势. 从理论上探讨这些自由基分子自旋耦合规律与NLO活性的关系, 为有机自由基NLO材料的分子设计与实验研究提供一定的理论依据.     

Fulvene,VII. Analyse der 13C- und 1H-NMR.-Spektren

Carbon-13 and proton NMR. spectra of pentafulvene and of a series of 6-substituted fulvenes have been analysed and assigned by homo- and heteronuclear double resonance and with the aid of iterative computation. ¹³C and ¹H chemical shifts are interpreted in terms of substituent effects and compared with π-electron charges calculated for the unsubstituted fulvene. From ¹³C shifts a 10 percent contribution of dipolar structures to the electronic configuration of fulvene may be estimated. All long-range proton-proton coupling constants including relative signs and some proton-carbon couplings in the fulvene spin system have been determined and assigned.     

The spin degeneracy problem in the AMO method

The use of different spin functions in the AMO method was investigated for benzene, the ring of six H atoms, and fulvene. The additional improvement in the energy obtained by the use of a linear combination of different spin functions is quite small for the singlet ground state. It is pointed out that there are great differences in energy between functions having the same spatial function but different spin functions.     

Nuclear spin selective alignment of ethylene and analogues

We investigate the alignment of ethylene and of some of its analogues via short, non-resonant laser pulses and show that it depends crucially on the nuclear spin of the molecules. We calculate the time-dependent alignment factors of the four nuclear spin isomers of ethylene and analyze them by comparison with the symmetric top molecule allene. Moreover, we explore how the nuclear spin selective alignment depends on the asymmetry of the molecules and on the intensity of the laser pulse. As an application, we discuss how nuclear spin selective alignment could be applied in order to separate different isotopomers of ethylene.     

An algorithm for the generation of nuclear spin species and nuclear spin statistical weights

This article develops a set of algorithms for the computer generation of nuclear spin species and nuclear spin statistical weights potentially useful in molecular spectroscopy. These algorithms generate the nuclear spin species from group structures known as generalized character cycle indices (GCCI s). Thus the required input for these algorithms is just the set of all GCCI s for the symmetry group of the molecule which can be computed easily from the character table. The algorithms are executed and illustrated with examples.     

Theoretical investigation of LaC3n+ (n = 0, 1, 2) clusters by density functional theory

LaC₃ⁿ⁺ (n=0, 1, 2) clusters have been studied using B3LYP (Becke 3-parameter–Lee-Yang-Parr) density functional method. The basis set is Dunning/Huzinaga valence double zeta for carbon and [2s2p2d] for lanthanum, denoted LANL1DZ. Four isomers are presented for each cluster; two of them are edge binding isomers with C_2v symmetry, the other two are linear chains with C_∞v symmetry. Meanwhile, two spin states for each isomer, that is, singlet and triplet for LaC₃⁺, doublet and quartet for LaC₃ and LaC₃²⁺, respectively, are also considered. Geometries, vibrational frequencies, infrared intensities, and other quantities are reported and discussed. The results indicate that at some spin states; the C_2v symmetry isomers are the dominant structures, while for the other spin states, linear isomers are energetically favored. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66 : 301–307, 1998     

Magnetic-field induced biaxiality in nematic liquid crystals. Consequences for nuclear spin relaxation

When a uniaxial nematic liquid crystal is subjected to a magnetic field making a non-zero angle with the C_∞ axis, the uniaxial symmetry is broken. The principal effect is a field-induced biaxiality in the long-wavelength region of the director fluctuation spectrum. Whereas the induced biaxiality has little effect on the mean square director fluctuation amplitudes 〈n²_x〉 and 〈n²_y〉, which are dominated by short-wavelength modes, it can profoundly affect the nuclear spin relaxation behaviour, which is sensitive to long-wavelength modes. Motivated by the increasing number of nuclear spin relaxation studies of director fluctuations in thermotropic, amphiphilic, and polymeric nematic liquid crystals, we present here a theoretical analysis of the effects of field-induced biaxiality on nuclear spin relaxation.     

Characterization of cationic diarylethene by electron spin resonance and absorption spectra-ratio of open/closed-ring isomers

Electrochemical cyclization/cycloreversion reactions of a diarylethene, 1,2-bis(3-methyl-2-thienyl)perfluorocyclopentene, are examined experimentally by electron spin resonance (ESR) and absorption spectra. To understand the ESR spectrum, the hyperfine coupling constants are calculated by the density functional theory (DFT) with the B3LYP exchange-correlation functional. The averaged values of the hyperfine coupling constants are approximated by imposing the C(2) symmetry on the structure of the diarylethene. We found that the spectral width of the ESR is significantly different between the open- and closed-ring isomers. This is due to the difference in the pi-conjugation between two isomers. The ESR spectral width analysis could, thus, be used to identify the isomerization of the radical species, which involve the change of the pi-conjugation. The experimentally observed spectrum is found to be the mixture of the open- and closed-ring isomers of the diarylethene. The excitation energies of the cationic diarylethenes are further identified by the SAC-CI calculations.     

An MNDO SCF MO investigation of some structural isomers of the perfluoro diazines (pyrimidine,pyrazine, and pyridazine) of relevance to their plasma polymerization

Extensive MNDO SCF MO calculations were made to determine the heats of formation of the ground state of geometry-optimized perfluorodiazabenzenes (pyridazine, pyrimidine, and pyrazine) and some of their structural isomers (Dewar benzene, benzvalene, prismane, fulvene, and hexadienyne). The heats of formation of the cation, singlet, and triplet states, were derived for the ground-state geometry of 1,3-diaza isomers to gain some insight into the excited state manifolds. These results were used to interpret various experimental observations that relate to the plasma polymerization of the diazines. In particular, the interconversion of the parent heteroaromatic, the relative energies of interconversion and polymerization, and the possibility of the elimination of a small stable molecule were considered. Comparison is made with results reported for the tetrafluorobenzenes.     

On the photomagnetism of nitronyl nitroxide, imino nitroxide, and verdazyl-substituted azobenzene

The cis- and trans-azobenzenes are known as photochromic isomers with the trans- converting into the cis-form and vice versa upon irradiation with specific wavelengths. We have quantum chemically investigated the cis- and trans-forms of substituted azobenzene diradicals, with two nitronyl nitroxides, imino nitoxides, or verdazyls at para positions and serving as monoradical centers, to determine whether they can exhibit a photoassisted magnetic crossover. Geometries of both substituted and unsubstituted molecules have been optimized by density functional (DF) method UB3LYP using the 6-311G(d,p) basis set. Optimization of the geometry of the cis isomers has required special care. Single point singlet, triplet, and broken symmetry calculations have been done using 6-311++G(3df, 3pd) basis set. The magnetic exchange coupling constants have been estimated from the broken symmetry calculations. Absorption wavelengths have been estimated for both substituted and unsubstituted species from time-dependent DF treatment using restricted spin-polarized methodology RB3LYP and 6-311++G(3df, 3pd) basis set. From the similarity in the calculated absorption wavelengths for the unsubstituted and substituted azobenzenes, and the increased oscillator strengths (f) for the substituted species, we predict that the diradical isomers would be strongly photochromic. From our triplet state and broken symmetry calculations, we predict that both the cis- and the trans-diradicals are antiferromagnetically coupled. This prediction is consistent with the spin alternation rule, and the possibility of a magnetic crossover is nonexistent for these species.     

The role of relaxation in the nuclear spin conversion process

The nuclear spin conversion rate depends on the collisions, which break the coherence created by magnetic intramolecular interactions between pairs of quasi degenerate levels belonging to the different spin isomers. The collisions act similarly to break the coherence created by a radiation field between two levels inducing pressure broadening of molecular transitions. Collisional relaxation rates have been extensively studied in this last situation using semi-classical approach and rectilign trajectory for collisional path.Taking advantage of the analogy, the present paper shows that calculations can be efficiently adapted for the collisional relaxation terms present in the ‘quantum relaxation’ model of nuclear spin conversion.For ¹³CH₃F, numerous experimental measurements of spin conversion rates in the presence of an electric field have allowed to derive directly relaxation rates. Our calculation appears to agree satisfactorily with these experimental values. For ¹²CH₃F, calculated relaxations rates are also given for the pairs involved in nuclear spin conversion.     

Physisorption and ortho–para conversion of molecular hydrogen on solid surfaces

Molecular hydrogen exists in nuclear-spin isomers of ortho and para species according to the total nuclear spin. These species are correlated to the rotational states with even and odd rotational quantum numbers because of the symmetry of the total wavefunction with respect to the permutation of the two nuclei. Although interconversion between the ortho and para states is extremely slow in an isolated state, the conversion is promoted in a physisorption state via interaction with surfaces of not only magnetic but also diamagnetic materials. In a physisorption state, the rotational motion of hydrogen molecules is modified due to the potential anisotropy. The physisorption properties and interconversion rate of the ortho and para hydrogen have recently been investigated on well-defined surfaces, which allow detailed comparison with theory. Furthermore, relative abundance of the ortho and para hydrogen in astronomical circumstances has been reported in recent years, which often shows a value out of equilibrium with the environment temperature. Physisorption and ortho–para conversion on the surfaces of interstellar media are expected to enable deeper understanding of astronomical phenomena. In this article, we review recent progress of experimental and theoretical studies on the physisorption and ortho–para conversion of molecular hydrogen and its relevance to the recent astronomical observation.     

Dynamic Nuclear Polarization in Suspensions Consisting of Xylene Isomers and Asphaltene Extracted from MC‐800 Liquid Asphalt

Overhauser effect type dynamic nuclear polarization experiments were performed to study suspensions of asphaltene in the xylene isomers (o‐, m‐, p‐) at a low magnetic field of 1.44 mT and three different temperatures (15, 25, and 35°C). The asphaltene was extracted from MC‐800 liquid asphalt. Intermolecular spin‐spin interactions occur between nuclear spins of hydrogen in the solvent medium and the free electron spins in the asphaltene micelles. The electron paramagnetic resonance spectrum of the asphaltene was obtained and the saturation experiments were applied to the samples prepared in vacuum. For all media, the dipole‐dipole interaction is predominant due to the negative signal enhancements. In all temperatures, the ultimate enhancement is the smallest for the p‐xylene solvent medium which has the lowest electrical dipole moment. The normalized low frequency relaxation components were calculated for 25°C, and the behavior of the nuclear‐electron coupling parameter according to this component is in agreement with the other works in the literature.     

2,3,5,6-Tetramethylmorpholine: II—1H n.m.r. structural studies of the isomers of 2,3,5,6-tetramethylmorpholine

The structures of the six isomers of 2,3,5,6-tetramethyl-morpholine have been determined by means of proton nuclear magnetic resonance studies at 100 MHz. The spectra have been analysed in terms of spin–spin coupling constants and population distributions of the possible conformers at low temperatures. Also included in this paper are results from n.m.r. studies on the six 4-benzyl-2,3,5,6-tetramethylmorpholine derivatives, which give information about the stereochemistry of the methyl groups α to the amine group.