一氧化碳E(1) Π态的意外预解离的解释。

Interpretation of the accidental predissociation of the E(1) Π state of CO.

作者信息

Majumder M, Sathyamurthy N, Vázquez G J, Lefebvre-Brion H

机构信息

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.

Instituto de Ciencias Físicas, Universidad Nacional Autónoma de México (UNAM), 62251 Cuernavaca, Mexico.

出版信息

J Chem Phys. 2014 Apr 28;140(16):164303. doi: 10.1063/1.4871109.

DOI:10.1063/1.4871109

PMID:24784266

Abstract

A special case of predissociation, known as indirect or accidental predissociation observed in the Rydberg E(1)Π bound state of CO is discussed. We resort to ab initio potentials in order to determine the plausible mechanism for this predissociation. Values of the predissociation width for the valence k(3)Π state of CO, as obtained from Fermi's golden rule, are also reported. The predissociation width obtained for the mixed E(1)Π (v = 1, J = 7) state is 0.033 cm(-1) compared to the experimental value of 0.034 cm(-1). The mixed E - E(') state with J = 28, v = 0 is found to be in near resonance condition with the k(3)Π (v = 4, J = 28) state, thus providing the means to indirect predissociation.

摘要

讨论了预解离的一种特殊情况，即在一氧化碳的里德堡E(1)Π束缚态中观察到的间接或偶然预解离。我们借助从头算势来确定这种预解离的合理机制。还报告了从费米黄金规则获得的一氧化碳价态k(3)Π态的预解离宽度值。对于混合的E(1)Π (v = 1, J = 7)态，获得的预解离宽度为0.033 cm⁻¹，而实验值为0.034 cm⁻¹。发现J = 28、v = 0的混合E - E(')态与k(3)Π (v = 4, J = 28)态处于近共振条件，从而为间接预解离提供了途径。