Mechanism and control of molecular energy flow: a modeling perspective

 Vibrational energy flow in organic molecules occurs by a multiple-time-scale mechanism that can be modeled by a single exponential only in its initial stages. The mechanism is a consequence of the hierarchical structure of the vibrational Hamiltonian, which leads to diffusion of vibrational wavepackets on a manifold with far fewer than the 3N−6 dimensions of the full vibrational state space. The dynamics are controlled by a local density of states, which does not keep increasing with molecular size. In addition, the number of vibrational coordinates severely perturbed during chemical reaction is small, leading to preservation of the hierarchical structure at chemically interesting energies. This regularity opens up the possibility of controlling chemical reactions by controlling the vibrational energy flow. Computationally, laser control of intramolecular vibrational energy redistribution can be modeled by quantum-classical, or by purely quantum-mechanical models of the molecule and control field. Received: 26 July 2002 / Accepted: 30 September 2002 / Published online: 2 December 2002 Electronic Supplementary Material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00214-002-0394-2. Acknowledgements. This work was supported by NSF grant CHE 9986670. Correspondence to: M. Gruebele e-mail: gruebele@scs.uiuc.edu     

Gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous solutions of Fe(II)–CDTA chelate complex

Utilization of ferric chelate complex of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA) for the oxidative scrubbing of H₂S and CH₃SH in Kraft mill streams can be beneficial from the standpoints of iron protection against precipitation and oxygen-mediated regenerative oxidation of the ferrous chelate CDTA. The physical solubility of methyl mercaptan in CDTA–Fe(III) complex cannot be measured directly because of oxidation of the sulfur-bearing gaseous species with the ferric chelate. Therefore, this investigation was carried out to determine the gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous iron-free CDTA solutions and non-reacting ferrous chelate solutions (CDTA–Fe(II) complex), using the static headspace method with an estimated accuracy of about 2%. Experiments with aqueous solutions of chelate concentrations varying between 38 and 300 mol m⁻³ were carried out at temperatures between 298 and 333 K and atmospheric pressure. It was shown that the methyl mercaptan solubility decreases with increasing temperature for all systems but was not much influenced, in the studied conditions, by the chelate concentration especially at larger temperatures.     

Analysis of RNA sequence structure maps by exhaustive enumeration I. Neutral networks

Summary Global relations between RNA sequences and secondary structures are understood as mappings from sequence space into shape space. These mappings are investigated by exhaustive folding of allGC andAU sequences with chain lengths up to 30. The computed structural data are evaluated through exhaustive enumeration and used as an exact reference for testing analytical results derived from mathematical models and sampling based on statistical methods. Several new concepts of RNA sequence to secondary structure mappings are investigated, among them that ofneutral networks (being sets of sequences folding into the same structure). Exhaustive enumeration allows to test several previously suggested relations: the number of (minimum free energy) secondary structures as a function of the chain length as well as the frequency distribution of structures at constant chain length (commonly resulting in generalized forms ofZipf's law).

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Analyse der Beziehungen zwischen RNA-Sequenzen und Sekundärstrukturen durch vollständige Faltung, 1. Mitt. Faltung, Neutrale Netzwerke

Zusammenfassung Die globalen Benziehungen zwischen RNA-Sequenzen und Sekundärstrukturen werden als Abbildungen aus einem Raum aller Sequenzen in einen Raum aller Strukturen aufgefaßt. Diese Abbildungen werden durch Falten aller binären Sequenzen desGC-undAU-Alphabets mit Kettenlängen bis zun=30 untersucht. Die berechneten Strukturdaten werden durch vollständiges Abzählen ausgewertet und als eine exakte Referenz zum Überprüfen analytischer Resultate aus mathematischen Modellen sowie zum Testen statistisch erhobener Proben verwendet. Einige neuartige Konzepte zur Beschreibung der Beziehungen zwischen Sequenzen und Strukturen werden eingehend untersucht, unter ihnen der Begriff derneutralen Netzwerke. Ein neutrales Netzwerk besteht aus allen Sequenzen, die eine bestimmte Struktur ausbilden. Vollständiges Abzählen ermöglicht beispielsweise die Bestimmung aller Strukturen minimaler freier Energie in Abhängigkeit von der Kettenlänge ebenso wie die Bestimmung der Häufigkeitsverteilungen der Strukturen bei konstanten Kettenlängen. Die letzteren folgen einer verallgemeinerten FormZipfschen Gesetzes.

     

耦合Gross-Pitaevskii方程的高效保质量守恒格式

该文为耦合Gross-Pitaevskii方程提出了一个新的保质量守恒格式.首先对空间导数利用高阶紧致格式离散得到半离散格式;然后在时间方向上利用基于外推的Crank-Nicolson格式离散,得到一个半显式的数值格式,然而此格式不能保持GP方程固有的质量守恒,因此,对格式得到的数值解利用投影方法进行修正,使其满足离散质量守恒;最后通过数值实验验证了该格式具有高精度以及保持质量守恒.     

西昌人工与自动酸雨观测记录差异规律研究

利用西昌国家基本气象站2021年人工和自动的酸雨观测数据,对TCYII 1型酸雨自动观测系统和人工系统的降水采样偏差及完整性、测量数据的准确性和一致性、设备硬件及软件通讯的故障率进行了对比分析。结果表明：正常情况下,2套系统数据的完整性、准确性、一致性较好。酸雨自动观测系统在采样方式及样品保存方面具备一定优势,能够保证观测数据更接近于自然雨水的数值,更贴近真实情况。自动观测系统面临单轨运行,它的手动操作设置、部分配件需厂家优化改进。上级主管部门对自动系统测量阈值的设定、采样中出现的漏采、空采、多采等特殊情况,仍需进一步明确处理办法。     

Range-Renewal Processes: SLLNs and Power Laws*

Given n samples(viewed as an n-tuple) of a γ-regular discrete distribution π,in this article the authors concern with the weighted and unweighted graphs induced by the n samples. They first prove a series of SLLN results(of Dvoretzky-Erd¨os’ type). Then they show that the vertex weights of the graphs under investigation obey asymptotically power law distributions with exponent 1 + γ. They also give a conjecture that the degrees of unweighted graphs would exhibit asymptotically power law distribu...     

Set controllability of Markov jump switching Boolean control networks and its applications

In this article, a novel method is proposed for investigating the set controllability of Markov jump switching Boolean control networks (MJSBCNs). Specifically, the switching signal is described as a discrete-time homogeneous Markov chain. By resorting to the expectation and switching indicator function, an expectation system is constructed. Based on the expectation system, a novel verifiable condition is established for solving the set reachability of MJSBCNs. With the newly obtained results on set reachability, a necessary and sufficient condition is further derived for the set controllability of MJSBCNs. The obtained results are applied to Boolean control networks with Markov jump time delays. Examples are demonstrated to justify the theoretical results.     

Event-triggered sliding mode control for switched genetic regulatory networks with persistent dwell time

This paper focus on the event-triggered sliding mode controller design for discrete-time switched genetic regulatory networks (GRNs) with persistent dwell time (PDT) switching. Firstly, the observation error dynamics of switched GRNs with PDT is constructed in the light of event-triggered sliding mode control (SMC) scheme. Next, sufficient conditions are derived to ensure the exponential stability of the augmented plant. Moreover, an event-triggered SMC law is synthesized to impel the system trajectories onto the sliding surface in a finite time. Finally, a verification example is provided to illustrate the effectiveness and potential of the proposed method.     

Study of the influence of physical aging on macroradical decay in poly(methyl methacrylate)

The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT _tr=68±1°C which are independent of thermal treatment. ForT<T _tr andT>T _tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk _{o, eff} andE _eff, was analyzed in terms of the so-called compensation quantitiesk _c andT _c and a proximity betweenT _c=T _tr andT _o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT _g.