Influence of Nonplanar Distortions of the Tetrapyrrole Macroring on the Electronic States of the Tetraphenylporphin Dication

Quantum-chemical calculations of the electronic structure of the tetraphenylporphin dication have been made by the CNDO/S method for various values of the parameter of saddle-like distortions of the porphyrin macroring of angle and the dihedral angle between the macroring planes and the phenyl rings. It is shown that the boundary highest occupied molecular orbital (HOMO) of symmetry a _2u is the most sensitive to variations in and and its order can be changed relative to another HOMO of symmetry a _1u . The behavior of the lower excited electronic singlet and triplet states depending on and has been analyzed in detail. In particular, the addition of configurations with charge transfer to the Q, B, and N states as well as to the T ₁ and T ₂ states has been determined quantitatively. An interpretation of the experimental spectra of porphyrin dications on the basis of the calculation results is given.     

Correlation inequalities for two-component hypercubicϕ 4 models

A collection of new and already known correlation inequalities is found for a family of two-component hypercubic ⁴ models, using techniques of duplicated variables, rotated correlation inequalities, and random walk representation. Among the interesting new inequalities are: rotated very special Dunlop-Newman inequality _1,x ² ; _1,z ² + _2g ² 0, rotated Griffiths I inequality _{1,x 1,y} ; _1z ² 0, and anti-Lebowitz inequalityu ₄ ¹¹¹¹ >-0.     

Differential equations in the spectral parameter,Darboux transformations and a hierarchy of master symmetries for KdV

We study a certain family of Schrödinger operators whose eigenfunctions (, ) satisfy a differential equation in the spectral parameter of the formB(, )=(x). We show that the flows of a hierarchy of master symmetries for KdV are tangent to the manifolds that compose the strata of this class ofbispectral potentials. This extends and complements a result of Duistermaat and Grünbaum concerning a similar property for the Adler and Moser potentials and the flows of the KdV hierarchy.     

Canonical linear transformation on fock space with an indefinite metric

We first construct a Fock space with an indefinite metric ,=( , ), where is a unitary and Hermitian operator. We define a -selfadjoint (Segal's) field (f) which obeys the canonical commutation relations (CCR) with an indefinite metric. We consider a transformation 349-2 (T = real linear) which leaves the CCR invariant. We investigate the implementability of T by an operator on the Fock space.     

Operator product expansions on the vacuum in conformal quantum field theory in two spacetime dimensions

Let ₁(x) and ₂(y) be two local fields in a conformal quantum field theory (CQFT) in two dimensional spacetime. It is then shown that the vector-valued distribution ₁(x)₂(y)|0 is a boundary value of a vectorvalued holomorphic function which is defined on a large conformally invariant domain. By group theoretical arguments alone it is proved that ₁(x)₂(y)|0 can be expanded into conformal partial waves. These have all the properties of a global version of Wilson's operator product expansions when applied to the vacuum state |0. Finally, the corresponding calculations are carried out more explicitly in the Thirring model. Here, a complete set of local conformally covariant fields is found, which is closed under vacuum expansion of any two it its elements (a vacuum expansion is an operator product expansion applied to the vacuum).Work supported by Deutsche Forschungsgemeinschaft     

Strict inequalities for some critical exponents in two-dimensional percolation

For 2D percolation we slightly improve a result of Chayes and Chayes to the effect that the critical exponent for the percolation probability isstrictly less than 1. The same argument is applied to prove that ifL():={(x, y):x=r cos, y=r sin for some r0, or} and():=limpp _c [log(p–p _c )]^–1 log P_cr {itO is connected to by an occupied path inL()}, then() is strictly decreasing in on [0, 2]. Similarly, lim_n [–logn]^–1 logP _cr {itO is connected by an occupied path inL()() to the exterior of [–n, n]×[–n, n] is strictly decreasing in on [0, 2].     

Internal Lifschitz singularities of disordered finite-difference Schrödinger operators

The integrated density of states has C-like singularities, ln|k(E)–k(E _c )|=–|E–E _c |^–v/2 _c (E), with _c >0, a milder function at the edges of the spectral gaps which appear when the distribution function of the potentiald has a sufficiently large gap. The behaviour of _c nearE _c is determined by the local continuity properties ofd near the relevant edge: _c (E)=O(1) ifd has an atom and =O(ln|E–E _c |) if is (absolutely) continuous and power bounded.     

The proper formula for relative entropy and its asymptotics in quantum probability

Umegaki's relative entropyS(,)=TrD (logD –logD ) (of states and with density operatorsD andD , respectively) is shown to be an asymptotic exponent considered from the quantum hypothesis testing viewpoint. It is also proved that some other versions of the relative entropy give rise to the same asymptotics as Umegaki's one. As a byproduct, the inequality TrA logAB TrA(logA+logB) is obtained for positive definite matricesA andB.     

On the asymptotics of occurrence times of rare events for stochastic spin systems

We consider translation-invariant attractive spin systems. LetT _,x ^v be the first time that the average spin inside the hypercube reaches the valuex when the process is started from an invariant measure with density smaller thanx. We obtain sufficient conditions for (1) ¦¦^–1 logT _,x ^v (x) in distribution as ¦¦ , and ¦¦^–1 logT _,x ^v (x) as ¦¦ , where (x):= –lim ¦¦^–1 log {(average spin inside ) x. And (2)T _,x ^v /ET _,x ^v converges to a unit mean exponential random variable as ¦¦ . Both (1) and (2) are proven under some type of rapid convergence to equilibrium. (1) is also proven without extra conditions for Ising models with ferromagnetic pair interactions evolving according to an attractive reversible dynamics; in this case is a thermodynamic function. We discuss also the case of finite systems with boundary conditions and what can be said about the state of the system at the timeT _,x ^v .On leave from São Paulo University.     

Melnikov's criterion for nondifferentiable weak-noise potentials

The stationary probability density of Fokker-Planck models with weak noise is asymptotically of the form exp[–1 /(q)]. If is smooth, it satisfies a Hamilton-Jacobi equation at zero energy and can be interpreted as the action of an associated Hamiltonian system. Under this assumption, has the properties of a Liapounov function, and can be used, e.g., as a thermodynamic potential in nonequilibrium steady states. We consider systems having several attractors and show, by applying Melnikov's method to the associated Hamiltonian, that in general is not differentiable. A small perturbation of a model with differentiable leads to a nondifferentiable . The method is illustrated on a model used in the treatment of the unstable mode in a laser.     

Diffraction of a plane wave in air by a cylindrical shell with two local masses

The diffraction of a plane wave by a cylindrical shell with two inertial masses attached symmetrically (at = ±₁) to its surface is investigated. The frequency response characteristics of the scattered field are calculated for a shell equipped with diametrically opposite masses (₁ = /2) and driven only by symmetric (about the plane =0, =) modes of vibration. It is established that the level of the scattered field in the interval of frequencies corresponding to even symmetric mode orders increases upon transition from the model with a single local mass (at =) to the model with two masses (at =±/2) (i.e., with a split inhomogeneity). At the frequencies of odd modes the scattered field coincides with the field of the homogeneous shell. The directivity patterns of the scattered field of a shell with two masses (at =±/2) are determined.Architecture and Construction Institute, Nizhegorod. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 37, No. 3, pp. 289–299, March, 1994.     

Generalization of the relativistic string model in the geometrical approach

We present a model of a one-dimensional extended relativistic object, whose motion is defined by the requirement that its time track in Minkowski space is a surface of the constant mean curvature H. The world surface of the relativistic string is a particular case of such surfaces, namely, a minimal surface with H=0. By differential-geometry methods the theory of the proposed object moving in three-dimensional space-time is reduced to one nonlinear equation – = Hsh. In the theory under consideration, there naturally arises the pair of Lax's operators needed to solve this nonlinear equation by the inverse scattering method.     

Empirical relations between noncommuting observables

A relation between noncommuting 1-0 quantum observables (i.e., projections) is introduced, being the state vector of the system. This relation extends the empirical implication between commuting projections. An operational interpretation of the new relation is given, which can be expressed also in counterfactual terms. It is shown that a relation proposed some years ago by Hardegree, namely the Sasaki arrow , can be interpreted in terms of the relation ; furthermore, this new relation turns out to be successful also in cases in which the Sasaki arrow fails.     

The Lipatov argument for φ 3 4 perturbation theory

We extend to ₃ ⁴ the work of S. Breen on the leading behavior at large order of ₂ ⁴ perturbation theory. Using a phase space expansion to obtain new estimates on the high energy behavior of ₃ ⁴ Feynman graphs, and a rigorous semiclassical expansion, we prove that the radius of convergence of the Borel transform of the pertubative series for ₃ ⁴ Euclidean field theory is the one computed by the Lipatov method.     

On the Nature of the “Low-Temperature Anomaly” in Metal–Semiconductor Schottky-Barrier Contacts

It is shown that the low-temperature anomaly of the I-V characteristics of homogeneous metal–semiconductor Schottky-barrier contacts (an increase in the ideality factor n and a decrease in the barrier height _bm, measured using the saturation current, with decreasing temperature, as well as the fact that their product _bn n_bm coincides very closely with the actual barrier height _b(V)) is a consequence of two factors: (1) the nonlinear dependence of the actual barrier height on the bias, resulting in an increase in the ideality factor with increasing bias voltage (current) and (2) measurement of the parameters n and _bm for the same current for all temperatures. A new expression for the flat-band barrier height _bf is derived.     

A new geometrical gravitational theory

A geometrical gravitational theory based on the connection ={ } + ln + ln –g ln is developed. The field equations for the new theory are uniquely determined apart from one unknown dimensionless parameter ₂. The geometry on which our theory is based is an extension of the Weyl geometry, and by the extension the gravitational coupling constant and the gravitational mass are made to be dynamical and geometrical. The fundamental geometrical objects in the theory are a metricg and two gauge scalars and. Physically the gravitational potential corresponds tog in the same way as in general relativity, the gravitational coupling constant to ^–2, and the gravitational mass tou(, ), which is a coscalar of power –1 algebraically made of and. The theory satisfies the weak equivalence principle, but breaks the strong one generally. We shall find outu(, )= on the assumption that the strong one keeps holding good at least for bosons of low spins. Thus we have the simple correspondence between the geometrical objects and the gravitational objects. Since the theory satisfies the weak one, the inertial mass is also dynamical and geometrical in the same way as is the gravitational mass. Moreover, the cosmological term in the theory is a coscalar of power –4 algebraically made of andu(, ), so it is dynamical, too. Finally we give spherically symmetric exact solutions. The permissible range of the unknown parameter ₂ is experimentally determined by applying the solutions to the solar system.     

Lorentz-symmetric solutions of nonlinear equations

Asymptotic properties of a real scalar self-interacting classical field depending on one variablez = t ²–x ² are studied. The field(z) approaches a minimum of the potentialU() for z + and a maximum forz– ifU((0)) is larger than two minima and smaller than two maxima ofU neighbouring to(0).Presented at the International Symposium Selected Topics in Quantum Field Theory and Mathematical Physics, Bechyn, Czechoslovakia, June 14–19, 1981.     

Multicomponent field theories and classical rotators

It is shown that aD-component Euclidean quantum field, =(¹,...,^D), with ||⁴+|²| interaction, can be obtained as a limit of (ferromagnetic) classical rotator models; this extends a result of Simon and Griffiths from the caseD=1. For these Euclidean field models, it is then shown that a Lee-Yang theorem applies forD=2 or 3 and that Griffiths' second inequality is valid forD=2; a complete proof is included of a Lee-Yang theorem for plane rotator and classical Heisenberg models. As an application of Griffiths' second inequality forD=2, an interesting relation between the parallel and transverse two-point correlations is obtained.Research supported in part by the National Science Foundation under grant NSF MPS 74-04870.     

On the geometric origin of the equation ϕ,11 — ϕ,22 = eϕ — e-2ϕ

It is shown that the equation ,11 — ,22 = e — e^-2 determines the intrinsic geometry of the two-dimensional affine sphere in the three-dimensional unimodular affine space like the sine-Gordon equation describes the metric on the surface of a constant negative curvature in the three-dimensional Euclidean space. The linear equations that determine the moving frame on the affine sphere are the Lax operators to the equation ,11 — ,22 = e — e^-2.     

Square root singularity in the viscosity of neutral colloidal suspensions at large frequencies

The asymptotic frequency, , dependence of the dynamic viscosity of neutral hard-sphere colloidal suspensions is shown to be of the form ₀A()(_p)^-1/2, whereA() has been determined as a function of the volume fraction , for all concentrations in the fluid range, ₀ is the solvent viscosity, and _p is the Péclet time. For a soft potential it is shown that, to leading order in the steepness, the asymptotic behavior is the same as that for the hard-sphere potential and a condition for the crossover behavior to 1/_p, is given. Our result for the hardsphere potential generalizes a result of Cichocki and Felderhof obtained at low concentrations and agrees well with the experiments of van der Werffet al. if the usual Stokes-Einstein diffusion coefficientD ₀ in the Smoluchowski operator is consistently replaced by the short-time self-diffusion coefficientD _s() for nondilute colloidal suspensions.