The visible spectrum of fulvene

Vapour phase and mixed crystal of the visible band system of fulvene are reported. The spectra show several interesting features including a main progression of 660 cm^?1 corresponding to the out-of-plane methylene twisting vibration. Strong Herzberg—Teller origins together with the breadth and overall diffuseness indicate two electronic states of symmetry A₁ and B₂ may be responsible for the observed spectrum. The spectra are blue shifted in going from the vapour to mixed crystal and show sequence structure to the blue of the main bands in the vapour phase.     

Theoretical study of the visible photodissociation spectrum of Ar3

The six A′ potential energy surfaces were computed by a DIM-like method involving a valence-bond quasidiabatic basis. Transition dipole moments were also determined using a similar method. The 4D dynamics of this system (restricted to a molecular plane fixed in space) was obtained with the HWD method (hemiquantal dynamics with the whole DIM basis) and the visible photoabsorption spectrum was determined with the help of a 1D full quantum mechanical program applied to each normal mode. The photoabsorption spectrum of Ar₃⁺ was calculated in the range 440–710 nm. It corresponds to photodissociation since the excited Ar₃⁺ ions almost all dissociate into the Ar⁺ +Ar+Ar channel by a rapid explosion of the cluster, and only very few into Ar₂⁺ +Ar. It is dominated by a transition to the second excited state along with a symmetric stretching motion. We found a prominent 80 nm wide peak centered at 530 nm, with a maximum cross section of 4.2 × 10⁻¹⁶cm². The Ar₂⁺ formation results from a transition to the first excited state under low-energy laser excitation and is controlled by non-adiabatic transitions.     

ExTTF-based dyes absorbing over the whole visible spectrum

New push-pull dyes featuring π-extended tetrathiafulvalene (exTTF) as the donor group and tricyanofuran (TCF) as the acceptor group were synthesized and characterized. Their broad absorption covers the entire visible spectral range and enters the near-infrared region. Electrochemistry and theoretical calculations provided an understanding of these singular electronic properties. The new dyes are appealing candidates as light harvesters in photovoltaic devices.     

Inherent homochirality of primary particles and meteorite impacts as possible source of prebiotic molecular chirality

A new hypothesis is presented that suggests super high velocity impacts (SHVI) of meteorites and collisions of other cosmic bodies as a universal source of nonracemic prebiotic organic matter. The hypothesis combines the notion by Davankov [29] on subatomic particles composing a homochiral pool of primary matter with the results by Managadze [49] on the synthesis of organic molecules in the plasma torch caused by a laser beam action on a solid target. The latter system serves as an adequate model for the plasma torch generated by SHVI of meteorites. New arguments are presented supporting the idea of inherent chirality of electrons and photons. Formation of chiral combinations of strong magnetic and electrostatic fields in the plasma torch is discussed, which could cause a chiral imbalance of molecules that self-assemble in the torch from the homochiral pool of atomic and subatomic species.     

激子手性方法用于多氧取代环己烯类化合物的研究

多氧取代环己烯是一类比较独特的天然产物,分子中多具有四个手性中心,立体化学多变,尽管用化学衍生物方法确定了部分化合物的绝对构型,但对已报道的化合物中仍有大部分未能确定其构型。在阐明分子相对构型的基础上,应用激子手性方法确定此类化合物的绝对构型,并利用Alchemy程序进行了分子动力学计算,对此类化合物的圆二色性规律进行了总结。     

Action spectra for modification of Escherichia coli B/r menaquinone by near-ultraviolet and visible radiations (313-578 nm)

–Menaquinone-8 (MQ-8) was irradiated in vivo in Escherichia coli B/r and in vitro after extraction from E. coli B/r, using monochromatic radiation in the range 313–578 nm. Within experimental error, the action spectra for loss of chromatographic mobility after irradiation in vivo and in vitro agree with each other and with the absorption spectrum of pure MQ-8. The MQ-8 is extremely sensitive to near-UV light (300–380 nm), showing an F₃₇in vivo at 334 nm of 1.3 kj/m², a value 15 times lower than that required for growth delay, and 150 times lower than that for killing, of E. coli B/r. The quantum yield for this reaction in vivo at 334 nm has the very high value of 0.26. The high sensitivity of MQ-8 suggests involvement in near-UV-induced effects on the plasma membrane.     

The visible spectrum of jet-cooled CF3NO

The electronic origin of the à A″ ← X̃ A′ transition of trifluoronitrosomethane (CF₃NO) has been reassigned to the very weak feature near 717.9 nm in the fluorescence excitation spectrum of the jet-cooled molecule. The prominent torsional progression has been reinpreted and the height of the threefold torsional barier in the Ã( n,π^* ) state has been revised to 601.5 ± 10 cm⁻¹.     

Theoretical study of the visible photodissociation spectrum of Ar 3 +

The photodissociation of Ar ₃ ⁺ is studied following a consistent theoretical approach from the Potential Energy Surfaces to the dynamics. Six P.E.S. are computed according to a D.I.M.-like model Hamiltonian. Transition dipole moments are determined using a similar method. The 4-D dynamics of this system is obtained with the H.W.D. method (Hemiquantal dynamic with the Whole DIM basis). All the 4 nuclear degrees of freedom and all the 6 electronic states are involved in the dynamical calculations, allowing for very general investigations. The main theoretical results are:

1. the spectrum essentially results from a Σ → Σg transition to the second excited electronic state along with a symmetric stretching motion
2. excited Ar ₃ ⁺ molecules almost all dissociate in Ar⁺ + 2 Ar
3. dissociation in Ar ₂ ⁺ + Ar requires special conditions such as low laser excitation and is predicted to increase with a specific excitation of the bending mode
4. the dominant symmetric stretching motion induces a bimodal kinetic energy distribution of the fragments.

All these points are in close agreement with experimental results.     

The visible spectrum of zirconium dioxide, ZrO2

The electronic spectrum of a cold molecular beam of zirconium dioxide, ZrO(2), has been investigated using laser induced fluorescence (LIF) in the region from 17,000 cm(-1) to 18,800 cm(-1) and by mass-resolved resonance enhanced multi-photon ionization (REMPI) spectroscopy from 17,000 cm(-1)-21,000 cm(-1). The LIF and REMPI spectra are assigned to progressions in the A?(1)B(2)(ν(1), ν(2), ν(3)) ← X?(1)A(1)(0, 0, 0) transitions. Dispersed fluorescence from 13 bands was recorded and analyzed to produce harmonic vibrational parameters for the X?(1)A(1) state of ω(1) = 898(1) cm(-1), ω(2) = 287(2) cm(-1), and ω(3) = 808(3) cm(-1). The observed transition frequencies of 45 bands in the LIF and REMPI spectra produce origin and harmonic vibrational parameters for the A?(1)B(2) state of T(e) = 16,307(8) cm(-1), ω(1) = 819(3) cm(-1), ω(2) = 149(3) cm(-1), and ω(3) = 518(4) cm(-1). The spectra were modeled using a normal coordinate analysis and Franck-Condon factor predictions. The structures, harmonic vibrational frequencies, and the potential energies as a function of bending angle for the A?(1)B(2) and X?(1)A(1) states are predicted using time-dependent density functional theory, complete active space self-consistent field, and related first-principle calculations. A comparison with isovalent TiO(2) is made.     

Microscale determination of the absolute configuration of alpha-aryl-substituted alcohols by the CD exciton chirality method

The absolute configurations of a broad spectrum of aryl alcohols 1 have been determined for the first time by the CD exciton chirality method. The configurational assignment is additionally verified by computer modeling and lipase-catalyzed acetylation of the racemic alcohols. The CD-spectroscopic data have revealed that the S enantiomers of the benzoate derivatives 2 display a positive first Cotton effect and the R enantiomers a negative one at around 228 nm. Thus, the sense of the first Cotton effect of the benzoate derivative 2 allows a reliable assignment of the absolute configuration of the corresponding alcohol 1.     

A CD exciton chirality method for determination of the absolute configuration of threo-beta-aryl-beta-hydroxy-alpha-amino acid derivatives

The absolute configuration of threo-beta-aryl-beta-hydroxy-alpha-amino acids was studied by CD exciton chirality method using 7-diethylaminocoumarin-3-carboxylate as a red-shifted chromophore. Bischromophoric derivatives for a series of threo-beta-aryl-beta-hydroxy-alpha-amino acids (3a-h) were prepared and their CD spectra measured in CH2Cl2. By combining the data of CD and NMR coupling constants, we are able to correlate their preferred conformer (B) and the positive CD to the corresponding (2S,3R)-absolute configuration. These results are consistent with those obtained from serine and threonine derivatives, which represent the simplest form of beta-hydroxy-alpha-amino acids. This CD method could thus become a general method for determining the absolute configuration of threo-beta-aryl-beta-hydroxy-alpha-amino acids.     

A study of the UV—visible absorption spectrum of molecular chlorine

The UV—visible absorption spectrum of molecular chlorine at 298 K was investigated in the wavelength range 200–550 nm with a spectral resolution of 0.2 nm. Except for minor discrepancies, the absorption cross-sections are in agreement with those found in the literature. In the region 250λ-550 nm, the Cl₂ spectrum can be adequately described by a semi-empirical function of the wavelength A (in vacuum) and temperature T

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where TANH=tanh(hcx559.751 cm⁻¹/2kT). The absorption of solar radiation by the weak continuum around λ_max=406.5 nm contributes 9% or more of the photodissociation of molecular chlorine in the atmosphere, but the banded Cl₂ features (λ 479 nm) are of negligible atmospheric significance.     

Isomeric structures and visible electronic spectrum of the C7H3 radicals

The 2-(buta-1,3-diynyl)cycloprop-2-yl-1-ylidene radical, a new three-membered ring chain with Cs symmetry, has been detected by electronic spectroscopy in the gas phase. The experimental investigation used a mass selective resonant two color two photon ionization technique coupled to a supersonic plasma source. Structures and relative stability energies of eight isomers of the C7H3 radical have been calculated. Based on the rotational analysis and the theoretical calculations, the observed spectrum is assigned as an 2A" <-- X2A' electronic transition of this exotic chemical species. This result shows that such a plasma source is a powerful tool to investigate intermediates involved in hydrocarbon chemistry as in flames.