线性响应和两种态特定方法模拟AF350电子跃迁的溶剂效应

在极化连续模型框架下比较了线性响应与两种不同态特定方法计算的溶液中Alexa Fluor 350(AF350)分子激发能和光谱移动值的差异. AF350的第一激发态S0→S1电子跃迁属于π→π^*跃迁, 主要对应于最高占据分子轨道(HOMO)到最低空轨道(LUMO)的跃迁. 该分子激发态偶极矩大于基态偶极矩, 激发态时溶质溶剂相互作用比基态时更强, 随着溶剂极性增大, 会发生光谱红移的现象. 与实验值相比, 线性响应和两种态特定方法均高估了激发能, 其中以IBSF(Improta-Barone-Scalmani-Frisch)方法得到的激发能最小, 矫正的基态反应场方法(cGSRF)得到的激发能最大. 对于光谱移动值, 3种方法与实验值相比都偏小, 线性响应方法(LR)计算出的误差最大, 而IBSF方法得到的结果与实验值最吻合, 是预测溶液中AF350分子激发能和光谱移动值最准确的方法. 对比了Marcus传统理论和基于约束平衡的非平衡溶剂化理论的结果, 发现后者得到的激发能和光谱移动值更接近于实验值.     

Theoretical examination of covalency in berkelium(IV) carbonate complexes

Experimental studies on the speciation of berkelium in carbonate media have shown that complexation of berkelium(III) by carbonate results in spontaneous oxidation to berkelium(IV) and that multiple species can be present in solution. We studied two proposed structures present in solution based on theoretical comparisons with spectroscopic data previously reported for Bk(IV) carbonate solutions. The multiconfigurational character of the ground and low-lying excited states in both complexes is demonstrated to result from the strong spin-orbit coupling. Although bonding in Bk(IV) carbonate and carbonate-hydroxide complexes is dominated by strong Coulombic forces, the presence of non-negligible covalent character is supported by ligand-field theory, natural localized orbitals, topological studies of the electron density, and energy transition state natural orbitals for chemical valence. Bond orders based on natural localized molecular orbitals show that Bk OH bonds possess enhanced orbital overlap, which is reflected in the bond strength. This is also observed in the decomposition of the orbital interaction energy into individual deformation density pairs.     

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Excimers and exciplexes are defined as assemblies of atoms or molecules A / A ′ where interatomic/intermolecular bonding appears only in excited states such as [ A ₂]* (for excimers) and [ AA ′]* (for exciplexes). Their formation has become widely known because of their role in gas‐phase laser technologies, but their significance in general chemistry terms has been given little attention. Recent investigations in gold chemistry have opened up a new field of excimer and exciplex chemistry that relies largely on the preorganization of gold(I) compounds (electronic configuration Au^I(5d¹⁰)) through aurophilic contacts. In the corresponding excimers, a new type of Au???Au bonding arises, with bond energies and lengths approaching those of ground‐state Au?Au bonds between metal atoms in the Au⁰(5d¹⁰6s¹) and Au^II(5d⁹) configurations. Excimer formation gives rise to a broad range of photophysical effects, for which some of the relaxation dynamics have recently been clarified. Excimers have also been shown to play an important role in photoredox binuclear gold catalysis.     

Quantum Information in Relativity: The Challenge of QFT Measurements

Proposed quantum experiments in deep space will be able to explore quantum information issues in regimes where relativistic effects are important. In this essay, we argue that a proper extension of quantum information theory into the relativistic domain requires the expression of all informational notions in terms of quantum field theoretic (QFT) concepts. This task requires a working and practicable theory of QFT measurements. We present the foundational problems in constructing such a theory, especially in relation to longstanding causality and locality issues in the foundations of QFT. Finally, we present the ongoing Quantum Temporal Probabilities program for constructing a measurement theory that (i) works, in principle, for any QFT, (ii) allows for a first- principles investigation of all relevant issues of causality and locality, and (iii) it can be directly applied to experiments of current interest.     

Aharonov–Bohm effect for bound states on spin-0 massive charged particles in a Gödel-type space–time with Coulomb potential

In this paper, we investigate the relativistic quantum dynamics of spin-0 massive charged particles in a Gödel-type space–time with electromagnetic interactions. We derive the radial wave equation of the Klein–Gordon equation with an internal magnetic flux field and Coulomb-type potential in the Som–Raychaudhuri space–time with cosmic string. We solve this equation and analyze the analog effect in relation to the Aharonov–Bohm effect for bound states.     

相对性区域创新指数与经济周期挖掘

提出了一类新的相对性区域创新指数,并采用世界专利申请数据对其进行了具体计算.基于区域创新同经济发展水平之间的超线性关系,该指数消除了经济发展水平对创新能力的影响,可以实现对不同发展水平的经济体之间进行有效的创新能力横纵对比.该创新指数尽管极其简单,却揭示出一系列迥异于传统认知的现象,例如中国大陆地区的技术创新能力在1980年代就已经位居世界前列.采用该指数,不但可以在较高水平上解释世界各国的经济增长,还发现它同经济增长率之间的相关性存在一个20年的经济周期.这些结果显示,该指数作为一个单一性指标,以极小的数据依赖就实现了较高程度的解释性,不但重新定位了世界各经济体的创新能力,对深入理解创新同经济发展之间的关系提供了新的角度,而且暗示着这类相对性经济指标的发展潜力与应用空间.     

Doublet bands at borders of A ≈ 130 island of chiral candidates: Case study of ~(120)I

Positive-parity doublet bands were reported in ~(120)I. Based on these, we discuss the corresponding experimental characteristics, including rotational alignment, and re-examine the corresponding configuration assignment.The self-consistent tilted axis cranking relativistic mean-field calculations indicate that the doublet bands are built on the configuration πh_(11/2)■νh_(11/2)~(-1). By adopting the two quasiparticles coupled with a triaxial rotor model, the excitation energies, energy staggering parameter S(I), B(M1)/B(E2), effective angles, and K plots are discussed and compared with available data. The obtained results support the interpretation of chiral doublet bands for the positive-parity doublet bands in ~(120)I, and hence identify this nucleus as the border of the A ≈ 130 island of chiral candidates.     

Approximate Atomic Green Functions

In atomic and many-particle physics, Green functions often occur as propagators to formally represent the (integration over the) complete spectrum of the underlying Hamiltonian. However, while these functions are very crucial to describing many second- and higher-order perturbation processes, they have hardly been considered and classified for complex atoms. Here, we show how relativistic (many-electron) Green functions can be approximated and systematically improved for few- and many-electron atoms and ions. The representation of these functions is based on classes of virtual excitations, or so-called excitation schemes, with regard to given bound-state reference configurations, and by applying a multi-configuration Dirac-Hartree-Fock expansion of all atomic states involved. A first implementation of these approximate Green functions has been realized in the framework of Jac, the Jena Atomic Calculator, and will facilitate the study of various multi-photon and/or multiple electron (emission) processes.     

A new set of atomic radii for accurate estimation of solvation free energy by Poisson–Boltzmann solvent model

The Poisson–Boltzmann implicit solvent (PB) is widely used to estimate the solvation free energies of biomolecules in molecular simulations. An optimized set of atomic radii (PB radii) is an important parameter for PB calculations, which determines the distribution of dielectric constants around the solute. We here present new PB radii for the AMBER protein force field to accurately reproduce the solvation free energies obtained from explicit solvent simulations. The presented PB radii were optimized using results from explicit solvent simulations of the large systems. In addition, we discriminated PB radii for N‐ and C‐terminal residues from those for nonterminal residues. The performances using our PB radii showed high accuracy for the estimation of solvation free energies at the level of the molecular fragment. The obtained PB radii are effective for the detailed analysis of the solvation effects of biomolecules. © 2014 The Authors Journal of Computational Chemistry Published by Wiley Periodicals, Inc.