通讯：振动激发的氢分子中量子化学的测试

Communication: Test of quantum chemistry in vibrationally hot hydrogen molecules.

作者信息

Niu M L, Salumbides E J, Ubachs W

机构信息

Department of Physics and Astronomy and LaserLaB, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.

出版信息

J Chem Phys. 2015 Aug 28;143(8):081102. doi: 10.1063/1.4929568.

DOI:10.1063/1.4929568

PMID:26328810

Abstract

Precision measurements are performed on highly excited vibrational quantum states of molecular hydrogen. The v = 12, J = 0 - 3 rovibrational levels of H2 (X(1)Σg (+)), lying only 2000 cm(-1) below the first dissociation limit, were populated by photodissociation of H2S and their level energies were accurately determined by two-photon Doppler-free spectroscopy. A comparison between the experimental results on v = 12 level energies with the best ab initio calculations shows a good agreement, where the present experimental accuracy of 3.5 × 10(-3) cm(-1) is more precise than theory, hence providing a gateway to further test theoretical advances in this benchmark quantum system.

摘要

对分子氢的高激发振动态进行了精密测量。H₂（X(1)Σg(+)）的v = 12，J = 0 - 3振转能级仅比第一解离极限低2000 cm⁻¹，通过H₂S的光解离来填充这些能级，并且利用双光子无多普勒光谱精确测定了它们的能级能量。v = 12能级能量的实验结果与最佳的从头计算结果之间的比较显示出良好的一致性，当前3.5×10⁻³ cm⁻¹的实验精度比理论更精确，从而为进一步检验这个基准量子系统中的理论进展提供了途径。