Path integral for the quartic oscillator: an accurate analytic formula for the partition function

IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Journal of Mathematical Chemistry Pub Date : 2024-09-20 DOI:10.1007/s10910-024-01671-z
Michel Caffarel
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Abstract

In this work an approximate analytic expression for the quantum partition function of the quartic oscillator described by the potential \(V(x) = \frac{1}{2} \omega ^2 x^2 + g x^4\) is presented. Using a path integral formalism, the exact partition function is approximated by the partition function of a harmonic oscillator with an effective frequency depending both on the temperature and coupling constant g. By invoking a Principle of Minimal Sensitivity (PMS) of the path integral to the effective frequency, we derive a mathematically well-defined analytic formula for the partition function. Quite remarkably, the formula reproduces qualitatively and quantitatively the key features of the exact partition function. The free energy is accurate to a few percent over the entire range of temperatures and coupling strengths g. Both the harmonic (\(g\rightarrow 0\)) and classical (high-temperature) limits are exactly recovered. The divergence of the power series of the ground-state energy at weak coupling, characterized by a factorial growth of the perturbational energies, is reproduced as well as the functional form of the strong-coupling expansion along with accurate coefficients. Explicit accurate expressions for the ground- and first-excited state energies, \(E_0(g)\) and \(E_1(g)\) are also presented.

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四次振子的路径积分:配分函数的精确解析公式
本文给出了用势\(V(x) = \frac{1}{2} \omega ^2 x^2 + g x^4\)描述的四次振子量子配分函数的近似解析表达式。使用路径积分的形式,精确配分函数由有效频率依赖于温度和耦合常数g的谐振子的配分函数近似。通过调用路径积分对有效频率的最小灵敏度原理(PMS),我们推导出一个数学上定义良好的配分函数解析公式。值得注意的是,该公式定性和定量地再现了精确配分函数的关键特征。在温度和耦合强度g的整个范围内,自由能精确到几个百分点。谐波(\(g\rightarrow 0\))和经典(高温)极限都完全恢复了。再现了弱耦合时基态能量幂级数的发散,其特征是微扰能量的阶乘增长,以及强耦合展开的函数形式以及精确系数。给出了基态和第一激发态能量\(E_0(g)\)和\(E_1(g)\)的精确表达式。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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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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