Rate constants of nonradiative intersystem crossing transition S1(ππ*) ? T1(ππ*) in molecules of aromatic compounds with heteroatoms

In terms of the adiabatic theory of interactions, we consider the results of the theoretical estimation of the rate constants K _ST of the nonradiative intersystem crossing conversion S ₁(ππ*) ⇝ T ₁ ^S (ππ*) for nine aromatic molecules containing 10–14 carbon atoms and one or two heavy (many-electron) oxygen or chlorine atoms.     

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.     

4氢-吡喃-4-硫酮1(n-π*),1Ag-(π→π*)和1Bu+(π→π*)等的激发态特征

理论上4氢-吡喃-4-硫酮的激发态特征用量子化学方法以及二维实空间分析法和三维立体实空间分析法加以研究.理论上的结果揭示1(n→π*)和1Ag-(π→π*)激发态是分子内电荷转移(ICT)激发态,而1Bu (π→π*)激发态是离域激发态.它们的跃迁偶极矩的强度和方向用三维密度跃迁(TD)加以解释,用三维电荷密度差(CDD)观察分子间电荷转移(ICT)的激发态特征或局部激发态特征.用二维实空间分析法研究电子.空穴相关性,离域化和激子的尺寸.     

A nonradiative intersystem crossing <Emphasis Type="Italic">S</Emphasis>(ππ*) ↝ <Emphasis Type="Italic">T</Emphasis>(ππ*) transition in dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxin

The probability of the nonradiative S-T intersystem crossing in dibenzo-p-dioxin is theoretically studied using a model for the vibronically induced spin-orbit coupling between electronic states and taking into account all out-of-plane vibrational modes. Several symmetry variants for the lowest S ₁(ππ*) singlet state are considered. In the case of g symmetry of this state, a provision is made for the possibility of its vibronic coupling with the nearest dipole-active singlet ¹ B _2u ππ* state. The rate constants K _ST of the S ₁ ? T(ππ*) transitions to the T ₁(³ B _3g ) state are estimated taking into account several intermediate triplet T _m (ππ*) states of g and u symmetry. For different symmetry types of the S ₁ state, the effect of K _ST on the fluorescence quantum yield ?_fl is discussed. The ¹ B _3g symmetry state is found to be the lowest S ₁ state. It is found that the main contribution to K _ST is made by the S ₁(¹ B _3g ) ? T ₄(³ A _g ) transition.     

4氢-吡喃-4-硫酮~1(n→π*),~1A_g~-(π→π*)和~1B_u~+(π→π*)等的激发态特征(英文)

理论上4氢-吡喃-4-硫酮的激发态特征用量子化学方法以及二维实空间分析法和三维立体实空间分析法加以研究.理论上的结果揭示^1（n→π^＊）和^1Ag^-（π→π^＊）激发态是分子内电荷转移（ICT）激发态,而^1Bu^＋（π→π^＊）激发态是离域激发态.它们的跃迁偶极矩的强度和方向用三维密度跃迁（TD）加以解释,用三维电荷密度差（CDD）观察分子间电荷转移（ICT）的激发态特征或局部激发态特征.用二维实空间分析法研究电子-空穴相关性,离域化和激子的尺寸.     

Nonfactorization and color-suppressedB →ψ(ψ′)+K(K*) decays

Using a value ofa ₂=0.1±0.03 in a formalism which usesN _c =3, we show that one can define an effectivea ₂, which includes the contribution of nonfactorized effects, for color-suppressed decayB→ψK. We determine the magnitude of this effectivea ₂, which is process-dependent and, in general, complex, in certain commonly used models of form factors. We analyze the color-suppressedB→ψK* branching ratio and longitudinal polarization and demonstrate that nonfactorization effects are needed to understand these data in certain commonly used models of form factors. We extend the analysis to color-suppressed decayB→ψ′K*, whereψ′=ψ(2S), and color-favored decay $\bar B^0 \to D^{* + } \rho ^ - $ where we demonstrate that factorization scheme works well.     

IDENTIFICATION AND SEPARATION OF THE TWO OVERLAPPING SINGLET 1(π, π*) ABSORPTION BANDS OF 1, 4-TETRACENEQUINONE

Absorption and fluorescence spectra of 1, 4-tetracenequinone (1, 4-TQ) have been measured in solution and the two overlapping 1(π, π^*) absorption bands with comparable intensities were separated. Based on the spectroscopic data, the energy levels of the low-lying 1(π, π^*) excited states of 6, 15-hexacenequinone were discussed in relation to those of 1, 4-TQ.     

Evidence for a new resonance Σ~* (1380) with J~P=1/2~(-*)

A new particle Σ * with J P = 1/2-was predicted by unquenched quark models with its mass around the well established Σ * (1385) with J P = 3/2 + .Here we re-examine some old data of the K￣p→Λπ*π + reaction.Firstly we re-fit the data for kaon beam momenta in the range of 1.0 - 1.8 GeV.Secondly we study the reaction at the energies around Λ*(1520) peak.Both studies show evidence for the existence of Σ*with J P = 1/2-around 1380 MeV.Higher statistic data on relevant reactions are needed to clarify the situation.     

Experimental review of e~+e~-→ππh_c

We review the recent BESIII measurement of e~+e~-→ππh_c in which its line shape is studied between the center-of-mass energies of 3.9 to 4.42 Ge V and an iso-vector charmonium-like state Z_c(4020) is observed in the invariant mass of πhc at the BESIII experiment. The charged Z_c(4020)~± is the second observed Z_c state following Z_c(3900), while the Z_c(4020)~0 is the first observed neutral Z_c state. The line shape of σ(e~+e~-→ππh_c) is also reanalyzed in view of searching for the Y state and the existence of the Y(4220) state is confirmed and compared with the previous work of the BESIII experiment.     

A theoretical prediction for exclusive decaysB→K(K*)η c

The decay rates for the exclusiveB decaysBK _c andBK* _c are calculated in the context of the heavy quark effective theory. We obtain(BK _c )/ (BK)=1.6±0.2 and(BK* _c )/ (K*)=0.39±0.04. These results lead to estimates BR(BK _c )=(0.11±0.02)% and BR(BK* _c )=(0.05±0.01)% if we use the central current experimental values forB(K, K ^*) branching ratios.     

Regge analysis of the ππ scattering amplitude

The theoretical predictions for the subtraction constants lead to a very accurate dispersive representation of the ππ scattering amplitude below 0.8 GeV. The extension of this representation up to the maximum energy of validity of the Roy equations (1.15 GeV) requires a more precise input at high energies. In this paper we determine the trajectories and residues of the leading Regge contributions to the ππ amplitude (Pomeron, f and ρ), using factorization, phenomenological parametrizations of the πN and NN total cross sections at high energy, and a set of sum rules which connect the high and low energy properties of ππ scattering. We find that nonleading Regge terms are necessary in order to achieve a smooth transition from the partial waves to the Regge representation at or below 2 GeV. We obtain thus a Regge representation consistent both with the experimental information at high energies and the Roy equations for the partial waves with ℓ≤4. The uncertainties in our result for the Regge parameters are sizable, but in the solutions of the Roy equations these only manifest themselves above the K[`]KK\hspace {0.03cm}\overline {\rule [0.7em]{0.6em}{0em}}\hspace {-0.8em}K threshold.     

New physics search in the doubly weak decay ■→K~+π~(-*)

The doubly weak transition b-dd■ is highly suppressed in the Standard Model,which makes it a potential channel for exploring new physics signals.We present a study of the exclusive two-body wrong sign weak decay ■→K+π-,which belongs to this class,in the perturbative QCD framework.We perform a model independent analysis for various effective dimension-6 operators for which large effects are possible.We further analyze the considered process in the Randall-Sundrum model,including the custodially protected and the bulk-Higgs Randall-Sundrum models.Exploring the experimentally favored parameter space of these models leads to a large and significant enhancement of the decay rate compared to the Standard Model,which might be accessible in future experiments.We propose to search for the wrong sign decay ■→K+π-via flavor-tagged time-dependent analyses,which can be performed at LHCb and Belle-Ⅱ.     

On puzzles and non-puzzles in B→ππ,πK decays

Recently, we have seen interesting progress in the exploration of CP violation in B⁰ _d→π⁺π^-: the measurements of mixing-induced CP violation by the BaBar and Belle collaborations are now in good agreement with each other, whereas the picture of direct CP violation is still unclear. Using the branching ratio and direct CP asymmetry of B⁰ _d→π^-K⁺, this situation can be clarified. We predict , which favours the BaBar result, and we extract γ=(70.0^+3.8 _-4.3)^°, which agrees with the unitarity triangle fits. Extending our analysis to other B→πK modes and B⁰ _s→K⁺K^- with the help of the SU(3) flavour symmetry and plausible dynamical assumptions, we find that all observables with colour-suppressed electroweak penguin contributions are measured to be in excellent agreement with the standard model. As far as the ratios R_c,n of the charged and neutral B→πK branching ratios are concerned, which are sizeably affected by electroweak penguin contributions, our standard-model predictions have almost unchanged central values but significantly reduced errors. Since the new data have moved quite a bit towards these results, the “B→πK puzzle” for the CP conserving quantities has been significantly reduced. However, the mixing-induced CP violation of B⁰ _d→π⁰K_S does look puzzling; if confirmed by future measurements, this effect could be accommodated through a modified electroweak penguin sector with a large CP violating new-physics phase. Finally, we point out that the established difference between the direct CP asymmetries of B^±→π⁰K^± and B_d→π^∓K^± appears to be generated by hadronic and not by new physics.     

The Torsion–Inversion Energy Levels in theS1(n, π*) Electronic State of Acetaldehyde from High-Resolution Jet-Cooled Fluorescence Excitation Spectroscopy

The laser-induced fluorescence excitation spectrum (LIF) of acetaldehyde that results from the emission from theS₁(n, π*) electronic state has been observed under very high resolution with a CW pulse-amplified laser under jet-cooled conditions. The origins of seven bands were determined by rotational analyses with a rigid-rotor Hamiltonian. The origins were fitted to a set of levels that were obtained from a Hamiltonian that employed flexible torsion–wagging large amplitude coordinates. The potential surface derived from the fitting procedure yielded barriers to torsion and inversion of 721.43 and 585.13 cm⁻¹, respectively. Minima in the potential hypersurface at θ = 58.6° and α = 35.7° defined the corresponding equilibrium positions for the torsion and wagging coordinates.     

K→(ππ)(I=2) decay amplitude from lattice QCD

We report on the first realistic ab initio calculation of a hadronic weak decay, that of the amplitude A(2) for a kaon to decay into two π mesons with isospin 2. We find ReA(2)=(1.436±0.063(stat)±0.258(syst))10(-8) GeV in good agreement with the experimental result and for the hitherto unknown imaginary part we find ImA(2)=-(6.83±0.51(stat)±1.30(syst))10(-13) GeV. Moreover combining our result for ImA(2) with experimental values of ReA(2), ReA(0), and ε'/ε, we obtain the following value for the unknown ratio ImA(0)/ReA(0) within the standard model: ImA(0)/ReA(0)=-1.63(19)(stat)(20(syst)×10(-4). One consequence of these results is that the contribution from ImA(2) to the direct CP violation parameter ε' (the so-called Electroweak Penguin contribution) is Re(ε'/ε)(EWP)=-(6.52±0.49(stat)±1.24(syst))×10(-4). We explain why this calculation of A(2) represents a major milestone for lattice QCD and discuss the exciting prospects for a full quantitative understanding of CP violation in kaon decays.     

从ψ’→J/ψπ~+π~-衰变中抽取ππ相移(英文)

ψ’→J/ψπ+π-提供了一个抽取低于0.59GeV的ππS波相移的新途径.基于在树图衰变振幅中忽略D波的近似,给出了从ψ’→J/ψπ+π-的ππ不变质量谱中得到ππS波相移的公式.     

N,N-二甲基硫代乙酰胺S3(ππ*)态的衰变动力学 (cited: 1)

采用共振拉曼光谱和完全活化空间自洽场方法研究了N,N-二甲基硫代乙酰胺在被激发至S₃(ππ^*)态后的衰减动力学. 指认了紫外吸收光谱和振动光谱. 获得了乙腈、甲醇和水溶剂中不同激发波长下的A带共振拉曼光谱,以探测Franck-Condon区域的结构动力学. 开展了CASSCF计算以确定低能单重激发态和锥形交叉点的电子激发能和优化几何结构. 通过共振拉曼强度分析和CASSCF计算获得了结构参数、A带结构动力学和S₃(ππ^*)态衰减机制. 提出了主要衰减通道为_3,FC(ππ^*)→S₃(ππ^*)/S₁(nπ^*)→_1(nπ^*).     

从ψ′→J/ψπ+π－衰变中抽取ππ相移

ψ'→J/ψ π+π-,提供了一个抽取低于,0.59GeV,的,ππ S,波相移的新途径.基于在树图衰变振幅中忽略,D,波的近似, 给出了从,ψ'→J/ψ π+π-,的\,ππ,不变质量谱中得到,ππ S,波相移的公式.     

从ψ＇→J/ψ π^＋π^- 衰变中抽取ππ相移

ψ＇→J/ψ π^＋π^-提供了一个抽取低于0．59GeV的ππ S波相移的新途径，基于在树图衰变振幅中忽略D波的近似，给出了从ψ＇→J/ψ π^＋π^-的ππ不变质量谱中得到ππ S波相移的公式。