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碱金属/稀有气体体系中卡弗速率的半经验理论。

Semiempirical theory of Carver rates in alkali/noble-gas systems.

作者信息

Camparo J C

机构信息

Electronics and Photonics Laboratory, The Aerospace Corporation, P.O. Box 92957, Los Angeles, California 90009, USA.

出版信息

J Chem Phys. 2007 Jun 28;126(24):244310. doi: 10.1063/1.2743958.

Abstract

During an encounter between a noble-gas atom and an alkali-metal atom, the electron density at the alkali nucleus is altered, resulting in a collisional change in the alkali's hyperfine coupling (i.e., AI.S-->(A+deltaA)I.S). In the case of binary encounters, this process has been termed the Carver mechanism. The short-lived collisional change in hyperfine coupling can have very noticeable effects: it plays an important role in the loss of nuclear spin polarization in high magnetic fields, and it can be one of the dominant line broadening mechanisms for alkali hyperfine transitions (e.g., in atomic clocks). Unfortunately, though there have been measurements of the Carver relaxation rate, to date there has been little theoretical analysis of the Carver mechanism, in large part due to the very difficult problem of computing deltaA. In the present work, the author develops a theory of the Carver rate based on a semiempirical expression for deltaA(r)/A, where r is the internuclear alkali/noble-gas separation, and validates the theory by comparing to experiment. This model is then used to compute Carver and Bouchiat relaxation rates (i.e., the three-body sticking-collision analog of the Carver rate) in diverse/alkali-noble gas systems. The main conclusion of this work is that Carver rates vary by orders of magnitude across the alkalies, and in general will likely only play a significant role for Rb and Cs noble-gas systems.

摘要

在稀有气体原子与碱金属原子相遇时,碱金属原子核处的电子密度会发生改变,导致碱金属超精细耦合发生碰撞变化(即,AI·S→(A + δA)I·S)。在二元相遇的情况下,这个过程被称为卡弗机制。超精细耦合中这种短暂的碰撞变化会产生非常显著的影响:它在高磁场中核自旋极化的损失中起重要作用,并且它可能是碱金属超精细跃迁的主要谱线展宽机制之一(例如,在原子钟中)。不幸的是,尽管已经对卡弗弛豫率进行了测量,但迄今为止,对卡弗机制的理论分析很少,很大程度上是因为计算δA是一个非常困难的问题。在本工作中,作者基于δA(r)/A的半经验表达式发展了一种卡弗速率理论,其中r是碱金属/稀有气体核间距,并通过与实验比较来验证该理论。然后使用这个模型来计算不同碱金属 - 稀有气体系统中的卡弗弛豫率和布希亚弛豫率(即卡弗速率的三体粘性碰撞类似物)。这项工作的主要结论是,卡弗速率在不同碱金属中变化几个数量级,并且一般来说,可能仅对铷和铯稀有气体系统起重要作用。

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