Optical properties of silylene-biphenylene copolymer films

We have measured absorption, photoluminescence, and photoluminescence excitation spectra, and the photoluminescence time response for films of silylene-biphenylene copolymer, ((C₆H₄)₂(Si(CH₃)₂)_m)_n with m=1,2,4, and 6. The excitation spectra clearly reveal that the lowest absorption band in each copolymer consists of two bands, i.e., a band at 4.7 eV and a band of which energy depends on m. Since the latter band is absent in the copolymer with m=1, the former band is attributed to the lowest π−π* transition in biphenylene subunits. The latter band is attributed to the lowest σ−σ* transition in the silylene subunits, considering its dependence on m. In contrast to the result for solution, the peak energy of photoluminescence band is independent of m. The band has a Stokes shift of more than 1 eV and a large band width of 0.5 eV. The time responses of photoluminescence intensity consist of more than two decay components and the intensity decays more slowly at smaller energy. The large Stokes shift is explained as due to excimer formation between biphenylene subunits. In order to explain the energy dependence of time responses, energy migration is discussed.     

Highly resolved electronic absorption and luminescence spectra of some phenanthrolines in Shpolskii matrices: Part II. Fluorescence and S1←S0 absorption spectra

Highly resolved fluorescence and S₁←S₀ absorption spectra of some phenanthrolines in n-alkane matrices were obtained at 77 K. The vibrational analysis of the spectra was carried out. Mirror symmetry distortions of the fluorescence and absorption spectra were attributed to vibronic coupling between ¹(π, π¹) states. It was shown that vibronic mixing of S₁(π, π¹) and S₂(π, π¹) states occurs in phenanthroline molecules with S₁-S₂ energy gap not exceeding 3000 cm^-1 (i.e., 4,7-, 1,7- and 1,10-Phen), whereas in other phenanthrolines the coupling of S₁ and S₃(π, π¹) plays a dominant role. Fluorescence quantum yields of phenanthroline liquid solutions were measured. Changes of luminescence efficiencies due to the change of the polarity of the media point to a weak coupling of the lowest ¹(π, π¹) and ¹(n, π¹) states.     

ESR Detection of Triplet States in Rare Earth Chelates

Abstract

Energy transfer from ligand molecule to ion in rare earth chelates has been assumed to involve a molecular triplet state. ^1,2 These triplet states manifest themselves optically as long-lived T_{π, π? →S}π,π emission if the lowest resonance level of the ion is of higher energy than the molecular triplet. ³ If the resonance level lies below the triplet, longlived emission is absent or severely reduced in intensity. ^4,5     

Electronic assignment as 1 A′(ππ*)-1 A′ of the 2980 Å system of 2-aminopyridine by rotational band contour analysis

In 2-aminopyridine the electronic origin band of the 2980 å electronic system, the longest wavelength system which has been observed, is shown to be a type B-type A hybrid band containing 55 ± 10 per cent of type A character. It follows that the electronic transition is ¹ A′-¹ A′ which implies a π*-π and not a π*-n electron promotion.

The degree of type A character is interpreted as indicating a swing of the transition moment by 10 ± 10° from the b axis of pyridine (the in-plane axis perpendicular to C ₂). Since it is expected that the first π*-π transition in pyridine has its transition moment polarized along the b axis the amino-group does not seem to perturb the pyridine transition strongly in this respect.

The changes of rotational constants from the ground to the excited state in 2-aminopyridine are very similar to those in aniline and probably reflect similar changes in geometry, namely a substantial contraction of the C-NH₂ bond, an opening of the internal ring angle adjacent to the substituent and a benzene-like expansion of the ring.

The origin of the 0-0 band is at 33471·1 ± 0·1 cm^-1.     

PDT光敏剂HA在不同液相体系下的光谱特性研究

为了对候选光敏剂竹红菌甲素(HA)进行改性并保持其优异的敏化特性,对HA的光谱特性和激发态性质作了进一步的指认。系统研究了HA在不同液相体系下的吸收和荧光光谱,对指认HA的光谱和电子跃迁的机制提出了新的依据,结果表明,吸收带I产生于π-π*跃迁,吸收带Ⅱ和Ⅲ产生于P-π共轭所导致的L→aπ跃迁的电子振动结构;荧光发射带I和Ⅱ是产生于同一跃迁机制S1(L,aπ)→S0的正常荧光的振动结构。     

Study of the π+π+π-π- system centrally 0 produced by incident π+ andp beams at 85 GeV/c

The reactions π⁺ p→π⁺(π⁺π⁺π^-π^-)p andpp→p(π⁺π⁺π^-π^-)p, where the (π⁺ π⁺ π^- π^-) system is centrally produced have been studied at 85 GeV/c. The π⁺π⁺π^-π^- mass spectrum shows evidence for thef ₁ (1285) meson with a mass of 1278±2 MeV and width 41±12 MeV which decays mainly through ρ⁰(770)π⁺π^-. Thef ₁(1285) is also observed in the ηπ⁺π^- channel. There is no significant evidence for ηππ or 4π decay modes of thef ₁(1420). The ρ⁰ρ⁰ production is found to be small. A Dalitz plot analysis of the 3π system shows evidence fora ₂ (1320) production and for a large contribution of theJ ^PC=1⁺⁺ ρπ wave.     

The lowest metal-to-bipyridine charge-transfer excited state of [Cr(2,2′-bipyridine)(CO)4]

The DV-Xα molecular-orbital calculations have been carried out on [Crbpy(CO)₄](bpy,2,2′-bipyridine) and its electron attachment and detachment products. The one-electron attachment of [Crbpy(CO)₄] yields a complex of bipyridine anion radical, while the one-electron detachment results in ionization of the central metal atom. The lowest excited state of [Crbpy(CO)₄] is the metal-to-ligand charge-transfer (MLCT) excited state which consists of the bipyridine anion radical and the central metal ionized. The transition-state calculation predicts the lowest MLCT excited states at around 23～30×10³ cm^?1 and the lowest bipyridine (π,π^*) excitations at 36×10³ cm^?1 and 42～45×10³ cm^?1. The calculation also concludes that the MLCT excitation induces a counter migration of the other electrons not directly involved in the charge-transfer excitation. The configuration-interaction calculations predict the lowest MLCT excited singlet states at around 21～35×10³ cm^?1 and the lowest bipyridine (π, π^*) excited singlet states at 42～62×10³ cm^?1, while the emissive lowest MLCT triplet state is at 17×10³ cm^?1. The transition moments evaluated with the transition-state wavefunctions can reproduce qualitatively the observed absorption spectral profile. The intensity of the MLCT transitions is obtained from the allowed (π, π^*) transitions of coordinated bipyridine but is not due to the intrinsic transition moments of MLCT excitations.     

Evidence that absorption in the π+ π− π− system in nuclear matter is stronger in the JP = 0− than in the JP = 1+ state

In the reaction π^? + A → π⁺π^?π^? + A at 15.1 GeV/c the coherently produced 3π mass spectrum has a broad peak around 1.1 GeV which consists mainly of a J^P = 1⁺ state and of a smaller fraction of 0^-. Comparing the observed dependence of the production of these diffractive states on the atomic weight A of the target nuclei with the optical model, we have studied the absorption of the produced states in nuclear matter. We have found the following values of the absorption cross-sections: σ₂(0^-) = 49_?7⁺⁹ mb and σ₂(1⁺) = 15.8_?1.3^+1.5 mb.     

Excitation of lowest electronic states of thymine by slow electrons

Excitation of lowest electronic states of the thymine molecules in the gas phase is studied by elec- tron energy loss spectroscopy. In addition to dipole-allowed transitions to singlet states, transitions to the lowest triplet states were observed. The low-energy features of the spectrum at 3.66 and 4.61 eV are identified with the excitation of the first triplet states 1₃ A′ (π → π*) and 1₃ A″ (n → π*). The higher-lying features at 4.96, 5.75, 6.17, and 7.35 eV are assigned mainly to the excitation of the π → π* transitions to the singlet states of the molecule. The excitation dynamics of the lowest states is studied. It is found that the first triplet state 1³ A′(π → π*) is most efficiently excited at a residual energy close to zero, while the singlet 2₁ A′(π → π*) state is excited with almost identical efficiency at different residual energies.     

Electronic states of SiF and SiF+: Configuration-interaction studies

For SiF, low-lying ²Π, ⁴Π, ²Σ⁺, ⁴Σ⁺, ²Σ⁻, ⁴Σ⁻, ²Δ, and ⁴Δ states were studied by configuration-interaction methods, using a double-zeta plus polarization basis set with 4s, 4pσ, 4pπ, and 5pπ Rydberg orbitals. Potential energy curves and spectroscopic constants for 17 stable valence and Rydberg states are given. The lowest ²Σ⁻ state is repulsive. There is good agreement with known spectroscopic constants. Besides A²Σ⁺, another semidiffuse state, 1⁴Π, is predicted. For the isoelectronic PO molecule, 2π → 3π valence excitations lie below Rydberg excitations, such that 2²Π of PO derives from 2π → 3π, whereas 2²Π of SiF derives from 3π → 4pπ. Dipole moments of X²Π and A²Σ⁺ at their respective R_e, and the radiative lifetime of A²Σ⁺ were calculated. For SiF⁺, many electronic states were investigated, but only two, the X¹Σ⁺ ground state and 1³Π are found to be stable. The ionization energy of SiF is calculated to be 6.87 eV (adiabatic) and 7.05 eV (vertical).     

The effect of the nature of peripheral platinated and bridging mercapto ligands on the optical and electrochemical properties of binuclear Pt(II) complexes with a metal-metal chemical bond

The effect of heterocyclic metalated and bridging ligands on the optical and electrochemical properties of [Pt(C^N)(μ-N^S)]₂ complexes ((C^N)^? and (N^S)^? are the deprotonated forms of 1-phenylpyrazole, 2-tolylpyridine, benzo[h]quinoline, 2-phenylbenzothiazole and 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptopyridine) is studied by ¹H NMR, electronic absorption, and emission spectroscopy, as well as by voltammetry. The long-wavelength spin-allowed (415–540 nm) absorption bands of the complexes are attributed to the metal-metal-to-ligand charge transfer (MMLCT) optical transitions. It is shown that the interaction of the d _Z2 and π _(C^N ^*) orbitals of two {Pt(C^N)} fragments of binuclear complexes leads to a cathodic shift (0.5–1.0 V) of their metal-centered oxidation potential and to an anodic shift (0.1–0.2 V) of their ligand-centered reduction potential with respect to [Pt(C^N)En]⁺ complexes. The luminescence of binuclear complexes in solutions at room temperature is assigned to the spin-forbidden MMLCT transition. It is shown that, in frozen (77 K) solutions, in addition to the MMLCT optical transitions, spin-forbidden radiative processes occur from the intraligand (π_(C^N)?π _(C^N) ^* ) and metal-to-ligand charge transfer (d_Pt?π _(C^N) ^* ) excited states.     

π+p→Λ+π+K反应共振—近阈效应关联的研究

本文建议作π+p→Λ+π+K反应的实验,其中质心系总能量固定为1900MeV。在末态K介子动能0—90MeV的变化范围内,观察末态Λ-π共振和在∑πk道产生阈附近的近阈效应。通过共振-近阈效应关联和共振的角分布可以确定Y₁^*的自旋和Y₁^*,和∑之间的相对宇称。按照先处理T短阵的么正性,后处理解析性的思想,本文引入了T矩阵在道空间上的对角表象。在此基础上,提出了唯象描述近阈效应、共振现象和末态相互作用,特别是近阈效应和在阈附近共振的关联的一个新方法。并且应用这个方法,处理了所建议实验中的末态共振-近阈效应关联。 关键词：     

On the structure of wave fields in the region of linear interaction between ordinary and extraordinary waves in two-dimensionally inhomogeneous magnetoactive plasmas

The spectra of the low-temperature photodissociation (photoionization) of Landau-Pekar polarons are calculated using the theory of quantum-coherent states and a new method of variation with respect to the parameters of phonon vacuum deformation. It is shown that the final polaron states upon photodissociation may have different numbers of phonons produced in a single dissociation event and different momenta of charge carriers. The spectrum of optical absorption related to the photodissociation of polarons exhibits a superposition of bands corresponding to various numbers of phonons formed as a result of dissociation of a single polaron. Due to a large width of the energy region corresponding to the final states of charge carriers, the halfwidth of each band is on the order of the energy of polaron coupling and is much greater than the phonon energy. For this reason, the individual phonon bands exhibit strong overlap. The very broad and, probably, structureless band formed as a result of the superposition of all these components begins at an energy equal to the sum of the polaron coupling energy (E _p) and the phonon energy. This band has a maximum at a frequency of about 5.6E _p/? and a halfwidth on the order of 5.6E _p/? at a unit effective mass (m* = m _e) of band electrons. For an effective charge carrier mass within m* = (1–3)m _e, the energy of the polaron band maximum can be estimated as 5E _p with an error of about 10%, and the halfwidth falls within 3.4E _p < ?Ω_1/2 < 5.6E _p. The multiphonon character of this band is related to a decay of the phonon condensate after the escape of charge carrier from a polaron. Such polarons are likely to be observed in the spectra of complex metal oxides, including high-temperature superconductors. Examples of such polaron bands in the reported absorption and photoconductivity spectra of nonstoichiometric cuprates, manganites, nickelates, and titanates are presented. A theory of the formation of Landau-Pekar polarons with the participation of branches of the polarization oscillations of the medium is developed. It is shown that, under certain conditions, such a multiphonon-dressed polaron can possess a coupling energy on the order of 0.2–0.3 eV, so that the maximum of the corresponding absorption band may occur at 1–1.5 eV.     

Studies of the temperature dependence of the phosphorescence spectra and decay rates of aromatic carbonyl molecules in mixed organic crystals

The temperature dependence of the phosphorescence spectra, decay rates and the S ₀ → T ₂(³ nπ*) absorption spectra were studied for aromatic carbonyl molecules in mixed organic crystals. The energy separation, ΔE_T , between the ³ ππ* lowest excited triplet (T ₁) states and the higher ³ π ^* states (T ₂) was estimated for several systems from the temperature dependence of the phosphorescence spectra and decay rates. It was found that the decay rates of the aromatic carbonyl molecules in the mixed crystal systems studied are determined by (1) thermal population to the ³ nπ* states and (2) increased radiationless transition rates at higher temperatures.     

The electronic spectrum of Dewar benzene

The electronic spectrum of Dewar benzene [bicyclo (2.2.0) hexa-2,5-diene] consists of two transitions above 185 nm. The lower energy transition is structureless and broad with a maximum at 205 nm. The other system begins around 200 nm and shows initially well-defined vibronic structure on a background of increasing continuous absorption, but becomes structureless by 185 nm. Arguments are presented that the two excited states involved in the spectrum are ¹A₂ arising from a $\text{π-π}{}^1$ excitation, and ¹B₁ from a $\text{σ-π}{}^1$ excitation involving the strained σ-bridge bond in Dewar benzene. The interrelationships both photochemical and photophysical of the (CH)₆ potential surface are discussed.     

Emission spectra of the cations of some fluoro-substituted phenols in the gaseous phase

Emission spectra of the cations of 2,5- and 3,5-difluorophenol, of 2,3,4- and 2,4,5-trifluorophenol, of 2,3,5,6-tetrafluorophenol and of 2,3,4,5,6-pentafluorophenol have been obtained in the gas phase using low-energy electron beam excitation. The band systems are assigned to the B?(π^?1) → X?(π^?1) electronic transitions of these cations by reference to photoelectron spectroscopic data. The He(Iα) photoelectron spectra and the ionisation energies of ten fluoro-substituted phenols are reported. The symmetries of the four lowest electronic states of these cations are inferred from the radiative decay studies. The lifetimes of the lowest vibrational levels of the B?(π^?1) state of the six fluoro-substituted phenol cations above have also been measured.     

Temperature dependence of the emission spectra of p-benzoquinone in a p-dichlorobenzene matrix

Emission and excitation spectra of p-benzoquinone have been measured in a partially translucent p-dichlorobenzene host matrix at different temperatures from 77 up to 323 K. Successive occurrence of the T₁(n,π^?) and T₂(n,π^?) phosphorescence and S₁(n,π^?) fluorescence has been observed for p-benzoquinone upon increasing temperature. The S₁–T₂ and T₂–T₁ energy separations determined from the temperature dependence of the emission intensities agreed well with those obtained from the locations of the T₁ and T₂ phosphorescence and S₁ fluorescence origins. Occurrence of the emission from S₁ and T₂ is brought by the thermal population from the T₁ state. The symmetries of the T₁ and T₂ states were determined to be B_1g and A_u, respectively, based on the spectral data.     

Kaon and pion ratio probes of jet quenching in nuclear collisions

Non-Abelian energy loss in quark gluon plasmas is shown to lead to novel hadron ratio suppression patterns in ultrarelativistic nuclear collisions. Here we investigate pion and kaon production in pp and AA collisions in a perturbative QCD frame, suppression pattern and hadron ratios. The K^?/K⁺ and K⁺/π⁺ ratios are found to be most sensitive to the opacity (density) of the plasma. Experimental data indicate that the fragmentation dominated pQCD region will be reached only at higher p _T; in an intermediate p _Tregion other particle production mechanisms dominate the K/π ratios.     

Optical and electrochemical properties of cyclometalated Pd(II) and Pt(II) complexes with a metal-metal chemical bond

Cyclometalated [M(C^N)(μ-(N-S))]₂ complexes ((M = Pd(II), Pt(II)), (C^N)^? are the deprotonated forms of 2-tolylpyridine and benzo[h]quinoline, and (N-S)^? are pyridine-2-thiolate and benzothiazole-2-thiolate ions) are studied by ¹H NMR, IR, electronic-absorption, and emission spectroscopy, as well as by voltammetry. It is shown that the formation of the metal-metal chemical bond and the σ _dz2 ^* orbital as a HOMO of complexes leads to the long-wavelength spin-allowed (410–512 nm) and spin-forbidden (595–673 nm) optical transitions σ _dz2 ^* ?π _(C^N) ^* in the absorption and phosphorescence spectra, as well as to the two-electron and successive one-electron oxidation with the formation of binuclear Pt(III) and Pd(III) complexes. The substitution of Pt(II) by Pd(II) is characterized by hypso- and bathochromic shifts of the spin-allowed and forbidden σ _dz2 ^* ?π _(C^N) ^* optical transitions in the absorption and phosphorescence spectra of complexes, by phosphorescence quenching of Pd(II) complexes in liquid solutions, and by an anodic shift of the oxidation potential of Pd(II) complexes compared with Pt(II) complexes.     

Ultra-violet absorption spectra and π-electron structures of nitromethane and the nitromethyl anion

The ultra-violet absorption spectrum of nitromethane was measured under various conditions. Besides the weak band at 270 mμ, a strong band, which may be regarded as due to the longest wavelength π→π* transition band, was observed at 198 mμ in the gaseous state. Further, the absorption spectrum of nitromethane was measured in aqueous solutions with several different ph values, and a strong band was observed at 233 mμ. From the fact that the pK_a value evaluated on the basis of the ph dependence of the absorption intensity is equal to that obtained electrometrically, it was concluded that the 233 mμ band is to be ascribed to the nitromethyl anion (H₂C^-NO₂). This band was found to shift to 238 mμ in alcoholic KOH solution.

The π-electron structure of the anion was studied theoretically by taking into account configuration interaction in terms of the ground, charge transfer, and locally excited configurations. It is shown that the 233 mμ band of the anion may be interpreted as an intramolecular charge-transfer absorption involving a large electron transfer from CH₂ ^- toward NO₂. It is suggested that electron donating substituent groups like NH₂, OH, and CH₂ ^- should cause the 198 mμ band of the nitro group to shift toward shorter wavelengths, in marked contrast to the case of substituted benzene molecules like aniline and phenol.