Analytic calculation of ground state splitting in symmetric double well potential

被引:21
|
作者
Sitnitsky, A. E. [1 ]
机构
[1] RAS, Kazan Inst Biochem & Biophys, FRC Kazan Sci Ctr, POB 30, Kazan 420111, Russia
关键词
Schrodinger equation; Confluent henu's function; Coulomb spheroidal function; FAR-INFRARED SPECTRA; VIBRATIONAL-SPECTRA; HYDROGEN-TRANSFER; ENERGY FUNCTION; RING COMPOUNDS; DYNAMICS; WKB; ANHARMONICITY; EQUATION; BAND;
D O I
10.1016/j.comptc.2018.05.021
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The exact solution of the one-dimensional Schrodinger equation with symmetric trigonometric double-well potential (DWP) is obtained via angular oblate spheroidal function. The results of stringent analytic calculation for the ground state splitting of ring-puckering vibration in the 1,3-dioxole (as an example of the case when the ground state tunneling doublet is well below the potential barrier top) and 2,3-dihydrofuran (as an example of the case when the ground state tunneling doublet is close to the potential barrier top) are compared with several variants of approximate semiclassical (WKB) ones. This enables us to verify the accuracy of various WKB formulas suggested in the literature: 1. ordinary WKB, i.e., the formula from the Landau and Lifshitz textbook; 2. Garg's formula; 3. instanton approach. We show that for the former case all three variants of WKB provide good accuracy while for the latter one they are very inaccurate. The results obtained provide a new theoretical tool for describing relevant experimental data on IR spectroscopy of ring-puckering vibrations.
引用
收藏
页码:15 / 22
页数:8
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