How to Predict Excited State Geometry by Using Empirical Parameters Obtained from Franck-Condon Analysis of Optical Spectrum

Excited state geometries of molecules can be calculated with highly reliable wavefunction schemes. Most of such schemes, however, are applicable to small molecules and can hardly be viewed as error-free for excited state geometries. In this study, a theoretical approach is presented in which the excited state geometries of molecules can be predicted by using vibrationally resolved experimental absorption spectrum in combination with the theoretical modelling of vibrational pattern based on Franck-Condon approximation. Huang-Rhys factors have been empirically determined and used as input for revealing the structural changes occurring between the ground and the excited state geometries upon photoexcitation. Naphthalene molecule has been chosen as a test case to show the robustness of the proposed theoretical approach. Predicted 1B_2u excited state geometry of the naphthalene has similar but slightly different bond length alternation pattern when compared with the geometries calculated with CIS, B3LYP, and CC2 methods. Excited state geometries of perylene and pyrene molecules are also determined with the presented theoretical approach. This powerful method can be applied to other molecules and specifically to relatively large molecules rather easily as long as vibrationally resolved experimental spectra are available to use.     

An Extremal Problem Arising in the Dynamics of Two-Phase Materials That Directly Reveals Information about the Internal Geometry

In two-phase materials, each phase having a non-local response in time, it has been found that for some driving fields the response somehow untangles at specific times, and allows one to directly infer useful information about the geometry of the material, such as the volume fractions of the phases. Motivated by this, and to obtain an algorithm for designing appropriate driving fields, we find approximate, measure independent, linear relations between the values that Markov functions take at a given set of possibly complex points, not belonging to the interval [-1,1] where the measure is supported. The problem is reduced to simply one of polynomial approximation of a given function on the interval [-1,1] and, to simplify the analysis, Chebyshev approximation is used. This allows one to obtain explicit estimates of the error of the approximation, in terms of the number of points and the minimum distance of the points to the interval [-1,1]. Assuming this minimum distance is bounded below by a number greater than 1/2, the error converges exponentially to zero as the number of points is increased. Approximate linear relations are also obtained that incorporate a set of moments of the measure. In the context of the motivating problem, the analysis also yields bounds on the response at any particular time for any driving field, and allows one to estimate the response at a given frequency using an appropriately designed driving field that effectively is turned on only for a fixed interval of time. The approximation extends directly to Markov-type functions with a positive semidefinite operator valued measure, and this has applications to determining the shape of an inclusion in a body from boundary flux measurements at a specific time, when the time-dependent boundary potentials are suitably tailored. © 2022 Wiley Periodicals, Inc.     

New asymptotic representations of the noncentral t-distribution

New asymptotic approximations of the noncentral t distribution are given a generalization of the Student's t distribution. Using new integral representations, we give new asymptotic expansions not only for large values of the noncentrality parameter but also for large values of the degrees of freedom parameter. In some cases, we accept more than one large parameter. These results are not only in terms of elementary functions, but also in terms of the complementary error function and the incomplete gamma function. A number of numerical tests demonstrate the performance of the asymptotic approximations.     

Multilevel-in-width training for deep neural network regression

A common challenge in regression is that for many problems, the degrees of freedom required for a high-quality solution also allows for overfitting. Regularization is a class of strategies that seek to restrict the range of possible solutions so as to discourage overfitting while still enabling good solutions, and different regularization strategies impose different types of restrictions. In this paper, we present a multilevel regularization strategy that constructs and trains a hierarchy of neural networks, each of which has layers that are wider versions of the previous network's layers. We draw intuition and techniques from the field of Algebraic Multigrid (AMG), traditionally used for solving linear and nonlinear systems of equations, and specifically adapt the Full Approximation Scheme (FAS) for nonlinear systems of equations to the problem of deep learning. Training through V-cycles then encourage the neural networks to build a hierarchical understanding of the problem. We refer to this approach as multilevel-in-width to distinguish from prior multilevel works which hierarchically alter the depth of neural networks. The resulting approach is a highly flexible framework that can be applied to a variety of layer types, which we demonstrate with both fully connected and convolutional layers. We experimentally show with PDE regression problems that our multilevel training approach is an effective regularizer, improving the generalize performance of the neural networks studied.     

Recoverable deformation and morphology after uniaxial elongation of a polystyrene/linear low density polyethylene blend

The transient recoverable deformation ratio after melt elongation at various elongational rates and maximum elongations was investigated for pure polystyrene and for a 85 wt.% polystyrene/15 wt.% linear low density polyethylene (PS/LLDPE 85:15) blend at a temperature of 170 ^oC. The ratio p of the zero shear rate viscosity of LLDPE to that of PS is p = 0.059 ≈ 1:17. Retraction of the elongated LLDPE droplets back to spheres and end-pinching is observed during recovery. A simple additive rule is applied in order to extract the contribution of the recovery of the elongated droplets from the total recovery of the blend. In that way, the recoverable portion of the PS/LLDPE blend induced by the interfacial tension is determined and compared with the results of a theory based on an effective medium approximation. The effective medium approximation reproduces well the time scale of the experimental data. In addition, the trends that the recoverable deformation increases with elongational rate and maximum elongation are captured by the theoretical approach.     

A brief review of the homotopy analysis method

本文简述同伦分析方法基本思想、最新理论进展及其在流体力学、固体力学、一般力学、量子力学、应用数学、金融等科学和工程领域的应用.同伦分析方法不依赖物理小参数, 适用范围更广,而且提供了一种简单的途径确保级数解收敛, 适用于强非线性问题.同伦分析方法已被成功应用于求解一些具有挑战性的力学问题,并获得一些全新的、 从未见报道的解. 这些成功的应用,证明了同伦分析方法的普遍有效性和原创性.     

Impact of singularity of Navier-Stokes equation upon atmospheric motion equations

Some conclusions about the smooth function classes stability for the basic system of equations of atmospheric motion and instability for Navier-Stokes equation are summarized. On the basis of this, by taking the basic system of equations of atmospheric motion via Boussinesq approximation as example to explain in detail that the instability about some simplified models of the basic system of equations for atmospheric motion is caused by the instability of Navier-Stokes equation, thereby, a principle to guarantee the stability of simplified equation is drawn in simplifying the basic system of equations.     

非惯性系下柔性悬臂梁的振动主动控制

采用变结构控制方法对非惯性系下柔性悬臂梁的振动主动控制进行研究．重点通过算例揭示一次近似模型与传统的零次近似模型的巨大差异，以及变结构方法在控制非惯性系下柔性悬臂梁的稳态振动的有效性．结果表明，当大范围旋转运动角速度较大时，传统零次近似模型不能对动力系统进行正确的数学描述；变结构控制方法能够使得非惯性系下梁的稳态振动得到完全镇定，且该方法对转动角速度变化具有较好的鲁棒性；采用零次近似模型进行控制设计的控制效果将在某一临界角速度条件下出现失效，该临界角速度值大于静止悬臂梁的基频．     

促进其线性频散特征另一种形式的Bousinesq方程

Ｂｏｕｓｉｎｅｓｑ方程能够用于模拟表面重力波传播过程中的折射、绕射、反射以及浅化，非线性作用等现象．用不同垂直积分方法所得到的二维Ｂｏｕｓｓｉｎｅｓｑ方程形式具有不同的线性频散特征．采用两个不同的水深层的水平速度变量组合，推导出一个新形式的Ｂｏｕｓｉｎｅｓｑ方程．通过对其参数的设置可得到精确的线性频散解Ｐａｄｅ近似４阶精度．其适用范围已由原来的浅水，向深水拓进．相速误差小于２％，其拓展适用范围可达到０８个波长水深．应用所得到的新型Ｂｏｕｓｉｎｅｓｑ方程，采用有限差分法，对经典工况进行了数值模拟，其计算结果表明，计算值与物模实验值吻合较好．这说明本文新形式的Ｂｏｕｓｓｉｎｅｓｑ方程对变水深非线性效应所产生的能量频散有着较为精确的描述