Accurate non-Born-Oppenheimer calculations of the lowest vibrational energies of D2 and T2 with including relativistic corrections

被引：19

作者：

Bubin, Sergiy ^{[1
]}

Stanke, Monika ^{[2
]}

Molski, Marcin ^{[3
]}

Adamowicz, Ludwik ^{[4
,5
]}

机构：

[1] Vanderbilt Univ, Dept Phys & Astron, Nashville, TN 37235 USA

[2] Nicholas Copernicus Univ, Dept Phys, PL-87100 Torun, Poland

[3] Adam Mickiewicz Univ Poznan, Fac Chem, Dept Theoret Chem, PL-60780 Poznan, Poland

[4] Univ Arizona, Dept Chem, Tucson, AZ 85721 USA

[5] Univ Arizona, Dept Phys, Tucson, AZ 85721 USA

来源：

CHEMICAL PHYSICS LETTERS | 2010年 / 494卷 / 1-3期

基金：

美国国家科学基金会;

关键词：

CORRELATED GAUSSIAN FUNCTIONS; HYDROGEN MOLECULE; RAMAN-SPECTROSCOPY; WAVE-EQUATION; SPECTRA; DEUTERIUM; SYSTEMS; GASES; H-2; D2;

D O I：

10.1016/j.cplett.2010.05.081

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：

In this work we report very accurate variational calculations of the two lowest vibrational states of the D-2 and T-2 molecules within the framework that does not assume the Born-Oppenheimer approximation. The non-relativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of alpha(2) calculated as expectation values of the operators representing these effects. The v = 0 -> 1 transition energy of D-2 obtained in the calculations is compared with the transition frequency obtained from the experimental spectra. The comparison shows the need to include corrections higher than second-order in alpha to further improve the agreement between the theory and the experiment. (C) 2010 Elsevier B.V. All rights reserved.

引用

页码：21 / 25

页数：5

共 34 条

[1]

ADAMOWICZ L, 1977, J CHEM PHYS, V67, P4298, DOI 10.1063/1.435370

[2] The vibrational g-factor of dihydrogen from theoretical calculation and analysis of vibration-rotational spectra [J].