Petersen Allan Christian
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark.
J Mass Spectrom. 2017 Dec;52(12):867-872. doi: 10.1002/jms.4022.
The correction term for the precursor ion signal width in determination of kinetic energy release is reviewed, and the correction term is formally derived. The derived correction term differs from the traditionally applied term. An experimental finding substantiates the inaccuracy in the latter. The application of the "T-value" to study kinetic energy release is found preferable to kinetic energy release distributions when the metastable peaks are slim and simple Gaussians. For electronically predissociated systems, a "borderline zero" kinetic energy release can be directly interpreted in reaction dynamics with strong curvature in the reaction coordinate.
回顾了在动能释放测定中前体离子信号宽度的校正项，并正式推导了该校正项。推导得到的校正项与传统应用的项不同。一项实验发现证实了后者的不准确。当亚稳峰狭窄且为简单高斯峰时，发现应用“T值”研究动能释放比动能释放分布更可取。对于电子预解离系统，“临界零”动能释放在反应动力学中可直接解释为反应坐标具有强烈曲率。
