Predissociation and photodissociation of IBr

The observed predominance of excited Br(² P _1/2) atoms in the nearultra-violet photodissociation products of IBr is shown to be quantitatively consistent with an intermediate coupling regime in the visible absorption region, which invalidates the traditional interpretation of the B′(O ⁺) state as a new Born-Oppenheimer state arising from a strongly avoided potential curve crossing. A general theory of predissociation at intermediate coupling, covering the positions, intensities and widths of the spectral lines, shows that both diabatic and adiabatic characteristics must be taken into account. The presence of a sharp level is predicted at any coincidence between an adiabatic and a diabatic term value with the same J value, and the spacing between neighbouring lines is shown to depend on an average between the diabatic and adiabatic rotational constants. The theory is successfully applied to the B(³Π _{o ⁺} ) and B′(O ⁺) states of IBr, and potential curves for the two states are reported. The analysis is consistent with the following curve crossing parameters r_x = 3·220 Å, E_x = 16 915 cm^-1, V ₁₂ = 170 cm^-1, and ΔF = 9178 cm^-1 Å^-1, and with the following spectroscopic constants for the B′(O ⁺) state of IBr⁷⁹:

     

CH3O (X2 E)中电子-振动-自旋耦合能级的理论计算

基于透热模型,采用量子化学从头计算法研究了CH₃O(X²E)自由基中电子-振动-自旋轨道相互作用.透热势能面通过CASPT2/cc-pVTZ方法计算获得.通过对比实验数据,计算得到的电子-振动-自旋能级较以往的报道获得了更精确的计算结果. 关键词： 透热模型 姜-泰勒效应 电子-振动-自旋耦合     

Nonadiabatic Predissociation Studies of the (1-3)Πg System of Al2 by Means of a Complex Rotated Finite Element Method

A general numerical Runge-Kutta-Fehlberg based diabatization procedure for electronic states in diatomics was applied to the adiabatic (1-3)³Π_g system of Al₂ in order to obtain a strictly diabatic basis. Using an exterior complex rotated finite element method, adiabatic Born-Oppenheimer (BO) as well as diabatic rovibronic term energy values and predissociation widths for the (2)³Π_g; (v, N)=(0−50, 0−25) and (3)³Π_g; (v, N)=(0−17, 0−25) levels were computed. Comparing rotationless BO and diabatic energies, differences between 10 and 25 cm⁻¹ are found for the (2)³Π_g levels while the (3)³Π_g levels display an almost constant shift ∼12 cm⁻¹. From the widths, the nonradiative lifetime for each rovibronic level was calculated. Based on existing rotationless radiative lifetimes, an estimation of an upper limit of about 50 ns was used to determine a number of rovibronic (2, 3)³Π_g levels which may be experimentally observed.     

On the possible perturbation of stratospheric dynamics due to Pinatubo aerosols

Summary The injection of a large amount of SO₂ in the tropical lower stratosphere following the eruption of Mt. Pinatubo (15.1^oN, 120.4^oE; June 15, 1991) can produce a not negligible perturbation in the stratospheric dynamics. Sulfate aerosols formed by nucleation of H₂SO₄ vapour, which is in turn produced from the SO₂ plume, are responsible for a net heating of the order of 0.15K/day in the equatorial stratosphere, located where the thickest portion of the aerosol cloud is found. As shown by recent satellite data, this diabatic perturbation is responsible for a temperature increase of the order of (2÷3) K at 30m bar during the summer and fall of 1991, that is similar to what found for the 1982 eruption of El Chichón. In this work we use a stratospheric three-dimensional model to investigate the dynamical response of the middle atmosphere to this diabatic forcing. Few months after the eruption, change in the diabatic circulation larger than 10% is found in the lower stratosphere, along with a stronger planetary wave activity during the 1991/92 winter season. This supports some conclusions of a recent investigation by Dunkerton and Delisi on the effects of the 1982 eruption of El Chichón and is shown to have a substantial effect on trace species transport, comparable to that associated to the Quasi-Biennal Oscillation (QBO).     

Semiempirical pseudopotential surfaces for chemical reactions: The (AB)+ X - dialkali halide systems

A generalization of the Roach-Child semiempirical pseudopotential calculation for K + NaCl to several analogous dialkali halide systems has been used to elucidate the chemical interactions governing the reaction dynamics. The Li + LiF ground-state potential surface, which exhibits a ～ 20 kcal/mole basin for isosceles Li₂F, is qualitatively similar to one obtained in a recent configurational interaction calculation. It is shown that regions of the Na₂Cl ground-state surface corresponding to Na₂ ⁺ interacting with Cl^- can be described in terms of an ion-pair Rittner potential model similar to that employed for the alkali halides. Chemical trends in the triangular complex well depths satisfactorily account for the experimentally observed transition between the collision complex mechanism (Rb + KCl) and the osculating complex model (Li + KBr) for the alkali-alkali halide exchange reactions at thermal energies. For collinear configurations with the alkalis on opposite ends, avoided intersections between the lowest two potential surfaces are characterized in terms of diabatic surfaces computed from truncated basis sets. Crossings of these surfaces account for the vibrational-electronic energy transfer between alkali atoms and vibrationally excited alkali halides. The ionic X ^- + A ₂ ⁺ potential surfaces are used to predict the product electronic excitation and partitioning of exoergicity in reactions of halogen atoms with alkali dimer molecules.     

Use of a diabatic molecular expansion in studies on electron capture by He2+ ions in helium at keV energies

In this preliminary work, using a 3-state diabatic molecular expansion without any excited channels, we have studied within the semiclassical impact parameter approximation the single charge transfer process He²⁺+He(1s ²)→He⁺(1s)+He⁺(1s). Our results agree very well with experiment, which demonstrates the usefulness of this type of diabatic molecular basis in doubly charged ion-atom collision systems.     

Delayed muon induced fission of209Bi and the role of meson-exchange currents

The probability for delayed muon induced fission of²⁰⁹Bi has been determined from a ( ^–,f ₁ f ₂) measurement. The measured fission probability P _f =(4.2±0.7)×10^–5 is compared with theoretical predictions. The high fission threshold reaction seems well suited for studying the influence of two-body meson-exchange currents in nuclear muon capture.We are indebted to the following institutes or organizations for financial support: Bundesministerium für Forschung und Technologie der Bundesrepublik Deutschland contract number 06 BN 271 (HP, PD, HH, FR, CR), Foundation for Fundamental Research on Matter (FOM) and the Netherlands Organization of the Advancement of Pure Research (NWO) (JK, CTAMdL, WL, AT) and the Schweizer Nationalfonds (LS).     

Preequilibrium emission in (p,x n) reactions on palladium isotopes

Energy spectra of neutrons from the^{104, 105, 106, 108, 110}pd(p, xn) reactions atE _p=26.1 MeV have been measured using the time-of-flight technique with good overall energy resolution (< 250=" kev).=" the=" hard=" part=" of=" angle-integrated=" spectra=" corresponding=" to=" low=" residual=" excitations=">U6MeV) exhibits pronounced structure varying from isotope to isotope. The observed structure can be reasonably well described by preequilibrium-model calculations with two-quasiparticle state densities for proton-particle neutron-hole configurations based on Nilsson-model single-particle levels instead of equidistant ones. The influence of nuclear deformation and pairing on preequilibrium particle emission is explored.Supported in part by the exchange program of the Universities of Hamburg and Zagreb, Internationales Büro — KFA Jülich, and by the BMFT (Contract 06 HH 142)     

Rovibronic Levels for the (1-3)Πg Manifold of B2: Exterior Complex Scaling Finite Element Calculations Based on an Adiabatic and a Strictly Diabatic Basis

A one-dimensional complex scaled finite element method was applied on an adiabatic basis of B₂ in order to find rovibronic term energy values for the (1)³Π_g; (v, N)=(0-8, 0-25) and (2)³Π_g; (v, N)=(0-10, 0-25) levels. The method was also applied to the (1)³Π_g; (v, N)=(0-8, 0-25) and (2)³Π_g; (v, N)=(0-1, 0-25) levels in a strictly diabatic framework. Adiabatic single-channel and diabatic coupled-channel total wavefunctions were obtained and used in order to identify the vibrational levels. Comparing levels for the interacting two-state (1-2)³Π_g and three-state (1-3)³Π_g system, a constant energy shift of about 1.7 cm⁻¹ is found. Comparisons between the adiabatic Born-Oppenheimer (BO) and the diabatic (1)³Π_g; (v, N)=(0-8, 0-25) levels show differences between −20 and 7 cm⁻¹, while the corresponding shifts for the (2)³Π_g; (v, N)=(0, 0-25) and (1, 0-25) levels are about 50 and 60 cm⁻¹, respectively. A comparison between our three-state approximation and experimental observations of the (2)³Π_g-A³Π_u electronic transition shows a difference in the line positions of about 665 cm⁻¹. The calculated widths for all but the (1)³Π_g; (v, N)=(7-8, 0-25), as well as the (2)³Π_g; (v, N)=(0, 0-25) BO and diabatic rovibronic levels, have small but with N increasing predissociation rates. The (1)³Π_g; (v>8, N=0-25) BO and the (2)³Π_g; (v, N)=(1, 0-25) diabatic levels are strongly predissociated with widths ≥16 cm⁻¹.     

Diabatization of the reactive F + H<Subscript>2</Subscript> system employing rigorous Berry phases

In this article are presented the first ever derived single-valued diabatic potentials for the reactive H₂ +  F system based on a rigorous study of the conical intersection (ci) and Born-Oppenheimer non-adiabatic coupling terms (BO NACTs). This study revealed the existence of a Jahn-Teller (1, 2) ci located at a point on the collinear axis and a Renner-Teller (2, 3) ci along this axis. The diabatic potentials were calculated employing the rigorous adiabatic-to-diabatic transformation (ADT) angles (also known as mixing angles) which possess integer Berry phases along any closed contour at the region of interest in configuration space. The ADT angles were calculated employing BO NACTs and line integrals.     

Coupled ab initio potential energy surfaces for the two lowest 2A′ electronic states of the C2H molecule

Realistic two-valued potential energy surfaces for the reaction C(³P) + CH(X²Π) → C₂ + H have been constructed from a set of high level ab initio data describing the first two ²A′ electronic states of the C₂H system. These states have linear equilibrium configurations, known as the X ²Σ⁺ and A²Π states, and are coupled by a conical intersection. They lead to the formation of C₂(X¹Σ⁺ _g) and C₂(a³Π_u) considering an adiabatic dissociation process. The ab initio calculations are of the multireference configuration interaction variety and were carried out using a polarized triple-zeta basis set. Using the ab initio adiabatic energies and the matrix elements of the dipole moment, a 2 × 2 diabatic representation of the electronic Hamiltonian was built. Each element of this Hamiltonian matrix was expressed within the double many-body expansion (DMBE) scheme which is based, in this case, on the extended Hartree-Fock approximate correlation energy model (EHFACE). The analytical adiabatic potential energy surfaces are then obtained as the eigenvalues of this matrix, and display correctly the Σ/Π conical intersection. Moreover, the non-adiabatic couplings given by our analytical model are compared with the ab initio ones, and good qualitative agreement is observed.     

Feasibility of similarity coefficient map in improving morphological evaluation of T2* weighted MRI for renal cancer

The purpose of this paper is to investigate the feasibility of similarity coefficient map (SCM) in improving morphological evaluation of T₂^* weighted (T₂^*W) magnatic resonance imaging (MRI) for renal cancer. Simulation studies and in vivo 12-echo T₂^*W experiments for renal cancers were performed for this purpose. The results of the first simulation study suggest that SCM can reveal small structures which are hard to be distinguished from the background tissue in T₂^*W images and the corresponding T₂^* map. The capability of improving morphological evaluation is likely due to the improvement in signal to noise ratio (SNR) and carrier to noise ratio (CNR) by SCM technique. Compared with T₂^*W images, SCM can improve SNR by a factor ranging from 1.87 to 2.47. Compared with T₂^* maps, SCM can improve SNR by a factor ranging from 3.85 to 33.31. Compared with T₂^*W images, SCM can improve CNR by a factor raging from 2.09 to 2.43. Compared with T₂^* maps SCM can improve CNR by a factor raging from 1.94 to 8.14. For a given noise level, the improvements of SNR and CNR depend mainly on the original SNRs and CNRs in T₂^*W images, respectively. In vivo experiments confirmed the results of the first simulation study. The results of the second simulation study suggest that more echoes are used to generate SCM, and higher SNR and CNR can be achieved in SCM. In conclusion, SCM can provide improved morphological evaluation of T₂^*W MR images for renal cancer by unveiling fine structures which are ambiguous or invisible in the corresponding T₂^*W MR images and T₂^* maps. What is more, in practical application, for a fixed total sampling time, one should increase the number of echoes as much as possible to achieve SCMs with better SNR and CNR.     

Experimental evidence for muonicX-rays from fission fragments

In the spectrum of muonic X-rays of²³⁸U measured in coincidence with prompt fission events a structure has been found which is attributed to 2p1s transitions of the muon attached to heavy fragments. The intensityI _s of this structure relative to the strengthI _pf observed for prompt fission has been determined to beI _s/I _pf=(6.0± 2.1) %. Although the experimental significance for the appeareance of this phenomenon is weak, this is the first experimental indication for its occuxence.We are indebted to the following institutes or organizations for financial support: Bundesministerium für Forschung und Technologie der Bundesrepublik Deutschland contract number 06BN271 (CR,PD,HH,FR,WS), Foundation for Fundamental Research on Matter (FOM) and the Netherlands Organization of the Advancement of Pure Research (NWO) (JK,CTAMdL,AT), the Swiss National Foundation (SNF) (LAS,LS), and the Heinrich-Hertz-Foundation (HH) (FFK,BS).     

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states of the C₂Br radical, correlating at linear geometries with ²Σ⁺ and ²Π states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, RCC=1.2621Å, R _CBr=1.7967Å, ∠ CCBr=156.1°, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C₂F and C₂Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Σ ,Π_1/2,Π_3/2 vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5 K have been calculated for the ¹² C¹² C⁷⁹Br isotopomer, to an upper limit of 2000 cm^?1, using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

Influence of the sample orientation in Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> crystals on the hydrostatic piezoelectric coefficients

The influence of the sample orientation on the effective value of the hydrostatic piezoelectric coefficients d _h ⁽ⁱ⁾ of Sn₂P₂S₆ crystals has been studied. The hydrostatic piezoelectric coefficients d _h ⁽¹⁾ and d′ _h ⁽³⁾ , were measured, d _h ⁽¹⁾ =(244±3) pC/N and d′ _h ⁽³⁾ =(92±1) pC/N. The hydrostatic piezoelectric coefficient d _h ⁽³⁾ for orthogonal axis system was calculated to be d _h ⁽³⁾ =(87±2) pC/N. The, optimal orientation of the sample has been found as (Xy l)−20°-cut. Maximal value of the effective hydrostatic piezoelectric coefficient d _h ⁽¹⁾ equals 260 pC/N. Double rotated samples were also studied. The orientation of the samples insensitive to the pressure has been found. The theoretical mean value of hydrostatic piezoelectric coefficient (d _h ) _mean corresponding to randomly oriented Sn₂P₂S₆ grains in a poled composite has been calculated to be (d _h ) _mean =136 pC/N.     

Rotational Analysis of the 1–4 Band of the B 2Σ+–X 2Σ+ System of 14C16O+

ABSTRACT

High-resolution emission spectrum of the 1–4 band of the B ²Σ⁺–X ²Σ⁺ transition of ¹⁴C¹⁶O⁺ was observed for the first time by conventional emission spectroscopy. The band spectrum was excited in a water-cooled Geissler lamp filled with commercial gaseous carbon monoxide enriched in about 80% of the radiocarbon ¹⁴C. A rotational analysis has been carried out and obtained molecular constants have been merged with previously published data for the B ²Σ⁺–A ²Π_i and A ²Π_i–X ²Σ⁺ transitions. The principal equilibrium constants for the ground X ²Σ⁺ state obtained from this work are ω_e = 2121.7726(98), ω_e x _e = 13.9055(27), B _e = 1.815290(30), α_e = 1.6594(33) × 10^?2, and γ_e = ? 0.377(73) × 10^?4 cm^?1. Also, presently known experimental equilibrium molecular constants of the X ²Σ⁺ states of the CO⁺ isotopic molecules are summarized and isotopic dependence of the B _e and ω _e constants is discussed.     

Investigation of the fusion of heavy nearly symmetric systems

Excitation functions in the vicinity of the Coulomb barrier have been measured for the formation of evaporation residues in¹⁰⁰Mo-induced fusion reactions with^{90, 92, 96}Zr,^{92, 96, 98, 100}Mo,¹⁰⁴Ru and¹¹⁰Pd as well as for the system⁹⁶Zr+⁹⁶Zr. From these data the fusion probability in central collisions was extracted covering a range of 4 orders of magnitude. At the fusion barriers expected from systematics we find that the fusion probability is suppressed by one to three orders of magnitude. It is rising very gradually at higher energies and reaches for the heaviest systems saturation only at energies as high as 30 MeV above the barrier. The observed hindrance of the fusion process increases roughly with the growing Coulomb repulsion between the collision partners, but there is also a distinct influence of their individual nuclear structure. The data are compared to the extra-push model, the surface-friction model and the diabatic fusion model. A parameterisation of the extra-push energy and its fluctuation in terms of a macroscopic quantity like the Coulomb repulsion combined with a microscopic quantity characterizing the nuclear structure is proposed. As a byproduct of this work a new alpha emitter,¹⁹¹Po, could be identified. Its half-life is (15.5 _–2.5 ⁺⁶ ) ms, the alpha energy is (7314±20) keV.