Stereoelectronic properties of photosynthetic and related systems: Ab initio configuration interaction calculations on the ground and lower excited singlet and triplet states of magnesium chlorin and chlorin

Ab initio configuration interaction wavefunctions and energies are reported for the ground state and many low-lying singlet and triplet states of magnesium chlorin and chlorin, and are employed in an analysis of the electronic absorption spectra of these systems.In chlorin, the calculated visible spectrum consists of two ${}^1\text{(π, π}{}^1\text{)}$ states, the lower energy, y-polarized state exhibiting moderate absorption intensity in contrast to the very weak absorption of the higher energy x-polarized state. The configurational composition of both states is well described by the four-orbital model. Five ${}^1\text{(π, π}{}^1\text{)}$ states are responsible for the Soret band envelope. A moderately intense y-state lies under the low energy edge of the band envelope, while two x-polarized states of moderate and strong intensity, respectively, are responsible for the band maximum. The final two ${}^1\text{(π, π}{}^1\text{)}$ states lie at the high energy edge of the Soret band and introduce a measure of asymmetry into the band envelope. Two ${}^1\text{(n, π}{}^1\text{)}$ states of very weak oscillator strength are also found in this region of the spectrum. All the Soret states are of complex configurational composition, and several of the higher lying states contain contributions from doubly excited configurations.The calculated visible spectrum of magnesium chlorin also consists of two ${}^1\text{(π, π}{}^1\text{)}$ states, with the weakly absorbing x-polarized state lying approximately 200 cm^?1 lower in energy than the moderately intense y-polarized state. The configurational composition of both states is well described by the four-orbital model. Four ${}^1\text{(π, π}{}^1\text{)}$ states constitute the bulk of the intensity in the Soret band envelope. In distinction to chlorin, the moderately intense ${}^1\text{(π, π}{}^1\text{)}$ state at the low energy edge of the band envelope is x-polarized. Two intense ${}^1\text{(π, π}{}^1\text{)}$ states of y- and x-polarization, respectively, constitute the band maximum region, and a single x-polarized state of moderately strong intensity can be assigned to the high energy shoulder of the band envelope. Two other weakly absorbing ${}^1\text{(π, π}{}^1\text{)}$ states are also found in this region, along with another weakly absorbing state of mixed in-plane and out-of-plane polarization. No clearly defined ${}^1\text{(n, π}{}^1\text{)}$ states are observed. As was the case for chlorin, all the Soret states are of complex configurational composition, and some of the higher energy states contain significant contributions from doubly excited configurations.Chlorin and magnesium chlorin both possess three ${}^3\text{(π, π}{}^1\text{)}$ states which lie below S₁ and a single ${}^3\text{(π, π}{}^1\text{)}$ which lies slightly above S₂. All four of the low-lying ${}^3\text{(π, π}{}^1\text{)}$ states in each molecule are well described by the four-orbital model, with T₁ being essentially a single configuration in each case. The remainder of the ${}^3\text{(π, π}{}^1\text{)}$ states are clustered in the same energetic region as the comparable ${}^1\text{(π, π}{}^1\text{)}$ Soret states, with comparably complex configurational compositions.Dipole moments and charge distributions for low-lying singlet and triplet states are also reported, and are used to rationalize chemical reactivity characteristics.     

SIMS and flash desorption studies of nickel oxygen interaction

O₂ exposure of polycrystalline nickel at 300 K results in characteristics changes of secondary ion emission. These can be described by a model which is in good agreement with corresponding LEED, AES, XPS, and ΔΦ results of other authors. According to this model, oxygen can be bonded on Ni in at least five different phases:

1. chemisorption, indicated by a rapid increase of Ni⁺, Ni ₂ ⁺ , and Ni₂O⁺ (≦5 L);
2. a rearranged chemisorption layer, characterized by a drastic decrease of Ni⁺, Ni ₂ ⁺ , and Ni₂O⁺ (5–15 L);
3. nickel oxide (NiO) responsible for a strong NiO^?- and NiO ₂ ^? -emission (≦40 L);
4. oxygen on top of this NiO layer, producing a final increase of Ni⁺ and NiO⁺ and a O₂-flash signal at 400 K (>40 L);
5. bulk dissolved oxygen in thermal equilibrium with a chemisorption layer (after several exposure/heating cycles).

During ion bombardment of a 100 L O₂ exposed Ni surface these different binding states occur in a reversed order of succession. O₂-flash signals at 400 and 1100 K, related to drastic changes in secondary ion emission at 400, 700, and 1100 K, reflect the disappearance of various oxygen binding states. The exchange between different oxygen phases was studied by¹⁶O₂/¹⁸O₂ isotope experiments.     

Salting-out chromatography : Aliphatic and polyglycol ethers,carboxylic acids by roger sargent and wm. rieman

Distribution ratios of 15 ethers were determined with various ammonium sulfate eluents and were used to determine the conditions necessary for the separation of five-and seven-component mixtures by salting-out chromatography. The application of this technique was found to be less successful than ion-exchange chromatography for the separation of carboxylic acids.     

On the ?ojasiewicz-Simon gradient inequality

We prove a general version of the ?ojasiewicz-Simon inequality, and we show how to apply the abstract result to study energy functionals E of the form

     

Upper limit for thermal direct photon production in heavy-ion collisions at 60 and 200A·GeV

The production of direct photons has been investigated in reactions ofp and¹⁶O projectiles at 60 and 200A·GeV with C and Au nuclei. Photon and ⁰ spectra have been measured in the pseudorapidity range 1.52.1 for the transverse momentum region 0.4 GeV/cp _T 2.8 GeV/c employing the lead-glass spectrometer SAPHIR. An upper limit of 15% at the 90% confidence level for the direct photon signal relative to the neutral pion production is obtained from the comparison of measured photon spectra with Monte Carlo simulations of the hadronic background based on the reconstructed yield of ⁰ and mesons. Consequences for a possible phase transition to a quark-gluon plasma are discussed.     

Collision-narrowing of Raman spectrum for spin-density fluctuations of electrons in n-GaAs

The inelastic light-scattering spectrum for single-particle excitations in n-GaAs has been found to be considerably $\text{narrower}$ than the Gaussian form usually predicted for a Maxwell-Boltzmann energy distribution. In this paper, we compare the contribution to the narrowing for two factors: collisions and the momentum-dependence of resonant enhancement terms. The analysis is restricted to the spin-density fluctuation mechanism, which has been found to be best suited for probing the electron distribution.     

Finite equational bases for congruence modular varieties

In this paper it is proved that a variety generated by a finite algebraic system with finitely many operations is finitely axiomatizable, provided that the variety is congruence modular and residually small. This result is an extension to congruence modular varieties of a well known theorem for congruence distributive varieties, due to K. A. Baker. Also, under somewhat less restrictive hypotheses, (which are satisfied by finite groups and rings) it is proved that a finite algebraic system belongs to a finitely axiomatizable locally finite variety.Research supported by National Science Foundation Grant No. DMS-8302295.Presented by George Gratzer.