Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30622, USA and Allen Heritage Foundation, Dickson, Tennessee 37055, USA.
J Chem Phys. 2019 Dec 28;151(24):244122. doi: 10.1063/1.5135721.
All reduced Wigner rotation matrix elements d (θ) can be evaluated very efficiently as a linear combination of either cos(Nθ) or sin(Nθ) terms as N runs in unit steps from either 0 or 12 to J. Exact, infinite-precision formulas are derived here for the Fourier coefficients in these d (θ) expressions by finding remarkable analytic solutions for the normalized eigenvectors of arbitrarily large matrices that represent the Ĵ angular momentum operator in the basis of Ĵ eigenstates. The solutions involve collections of numbers W for (m, n) = (J-M, J-N) ∈ [0, 2J] that satisfy the recursion relation (m+1)W -2(J-n)W +(2J-m+1)W =0. These quantities, designated here as Wigner numbers, are proved to be integers that exhibit myriad intriguing mathematical properties, including various closed combinatorial formulas, (M, N) sum rules, three separate M-, N-, and J-recursion relations, and a large-J limiting differential equation whose applicable solutions are products of a polynomial and a Gaussian function in the variable z = -2(J + 1)M. Accordingly, the Wigner numbers constitute a new thread of mathematics extending outside the context of their immediate discovery. In the midst of the W proofs, a class of previously unknown combinatorial summation identities is also found from Wigner number orthonormalization conditions.
所有的约化维格纳旋转矩阵元 $d(\theta)$ 都可以非常有效地作为从 0 或 12 到 J 的单位步长的 N 的余弦或正弦项的线性组合来评估。通过找到代表 J 角动量算符在 J 本征态基中的任意大矩阵的归一化本征向量的显著解析解,这里推导出了这些 $d(\theta)$ 表达式中的傅里叶系数的精确、无限精度公式。解涉及到满足递归关系 $(m+1)W-2(J-n)W+(2J-m+1)W=0$ 的数 $W$ 的集合,对于 $(m,n)=(J-M,J-N)\in[0,2J]$。这些数量,这里指定为维格纳数,被证明是整数,表现出无数有趣的数学性质,包括各种封闭的组合公式、(M,N)求和规则、三个单独的 M、N 和 J 递归关系,以及一个大 J 极限微分方程,其适用的解是多项式和变量 z=-2(J+1)M 中的高斯函数的乘积。因此,维格纳数构成了一条新的数学线索,延伸到它们的直接发现之外。在 W 的证明过程中,还从维格纳数正交归一化条件中找到了一类以前未知的组合求和恒等式。