线性响应函数 $$chi (\textbf{r}, \textbf{r}^{'})$$ :另一种视角

IF 1.7 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Journal of Mathematical Chemistry Pub Date : 2024-02-22 DOI:10.1007/s10910-024-01578-9
Samir Kenouche, Jorge I. Martínez-Araya
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引用次数: 0

摘要

在本文中,我们提出了一种概念方法来为非局部函数 \(\chi (\textbf{r}, \mathbf{r'})\) 赋予 "数学意义"。由于这个核是一个取决于六个直角坐标的函数,因此对它进行数学评估仍然很困难。这种方法背后的想法是寻找一个极限过程,以便从数学上探索这个非局部函数。根据我们的方法,bra (\langle \chi ^{\xi }_{r'} \vert \)是线性函数,它对应于任意 ket \(\vert \psi \rangle \),值 \(\langle \textbf{r}' \vert \psi \rangle \)。用浓缩的写法来写\(\langle \chi ^{\xi }_{r'}\vert \, \langle \textbf{r}\vert \psi \rangle = \langle \textbf{r}' \vert \psi \rangle \),而这是通过利用德尔塔函数的筛分特性实现的,该特性使德尔塔函数具有度量的意义,即度量在点\(\textbf{r}'\)上的\(\psi (\textbf{r})\) 的值。值得注意的是\(\langle \chi ^{\xi }_{r'} \vert \)不是一个算子,因为当它应用在一个ket上时,它产生的是\(\psi (\textbf{r} = \textbf{r}')\) 而不是一个ket。量 \(\chi ^{\xi }_{r'} (\textbf{r})\) 作为新生德尔塔函数进行,在 \(\xi \rightarrow 0\) 的极限处变成实德尔塔函数。在这方面,\(\chi ^{\xi }_{r'} (\textbf{r})\) 在卷积积分过程中充当了积分算子核的极限。
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The linear response function \(\chi (\textbf{r}, \textbf{r}^{'})\): another perspective

In this paper, we propose a conceptual approach to assign a “mathematical meaning” to the non-local function \(\chi (\textbf{r}, \mathbf{r'})\). Mathematical evaluation of this kernel remains difficult since it is a function depending on six Cartesian coordinates. The idea behind this approach is to look for a limit process in order to explore mathematically this non-local function. According to our approach, the bra \(\langle \chi ^{\xi }_{r'} \vert \) is the linear functional that corresponds to any ket \(\vert \psi \rangle \), the value \(\langle \textbf{r}' \vert \psi \rangle \). In condensed writing \(\langle \chi ^{\xi }_{r'} \vert \, \langle \textbf{r} \vert \psi \rangle = \langle \textbf{r}' \vert \psi \rangle \), and this is achieved by exploiting the sifting property of the delta function that gives it the sense of a measure, i.e. measuring the value of \(\psi (\textbf{r})\) at the point \(\textbf{r}'\). It is worth noting that \(\langle \chi ^{\xi }_{r'} \vert \) is not an operator in the sense that when it is applied on a ket, it produces a number \(\psi (\textbf{r} = \textbf{r}')\) and not a ket. The quantity \(\chi ^{\xi }_{r'} (\textbf{r})\) proceed as nascent delta function, turning into a real delta function in the limit where \(\xi \rightarrow 0\). In this regard, \(\chi ^{\xi }_{r'} (\textbf{r})\) acts as a limit of an integral operator kernel in a convolution integration procedure.

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来源期刊
Journal of Mathematical Chemistry
Journal of Mathematical Chemistry 化学-化学综合
CiteScore
3.70
自引率
17.60%
发文量
105
审稿时长
6 months
期刊介绍: The Journal of Mathematical Chemistry (JOMC) publishes original, chemically important mathematical results which use non-routine mathematical methodologies often unfamiliar to the usual audience of mainstream experimental and theoretical chemistry journals. Furthermore JOMC publishes papers on novel applications of more familiar mathematical techniques and analyses of chemical problems which indicate the need for new mathematical approaches. Mathematical chemistry is a truly interdisciplinary subject, a field of rapidly growing importance. As chemistry becomes more and more amenable to mathematically rigorous study, it is likely that chemistry will also become an alert and demanding consumer of new mathematical results. The level of complexity of chemical problems is often very high, and modeling molecular behaviour and chemical reactions does require new mathematical approaches. Chemistry is witnessing an important shift in emphasis: simplistic models are no longer satisfactory, and more detailed mathematical understanding of complex chemical properties and phenomena are required. From theoretical chemistry and quantum chemistry to applied fields such as molecular modeling, drug design, molecular engineering, and the development of supramolecular structures, mathematical chemistry is an important discipline providing both explanations and predictions. JOMC has an important role in advancing chemistry to an era of detailed understanding of molecules and reactions.
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