Relativistic effects in the gas-phase molecular hydration of heavy atomic transition metal cations (Groups 10–12): Group variations in energetics and kinetics
IF 1.6 3区 化学Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
{"title":"Relativistic effects in the gas-phase molecular hydration of heavy atomic transition metal cations (Groups 10–12): Group variations in energetics and kinetics","authors":"Voislav Blagojevic , Diethard K. Böhme","doi":"10.1016/j.ijms.2024.117371","DOIUrl":null,"url":null,"abstract":"<div><div>We assess relativistic effects in the molecular hydration of late atomic transition metal cations (Groups 10–12) as revealed by a review of previously published experimental and theoretical hydration energies and by kinetic measurements at room temperature. To fill gaps in theoretical hydration energies, we report here newly computed hydration energies, with and without relativistic effects, for all 9 atomic transition metal ions in the three Groups using DFT and RI-MP2 theory. Rate coefficients are taken from previous work in our laboratory and we provide here, for the first time, the raw experimental data for the kinetics of all 9 hydration reactions. Trends in hydration energies and hydration kinetics are inspected and compared going down the Periodic Table. We find a strong 3rd-row enhancements in the hydration energy and the rate of hydration and these are attributed to relativistic contributions to the bonding of H<sub>2</sub>O to the 3rd-row transition metal cations. This behaviour is very much in line with that reported earlier with other molecular ligands.</div></div>","PeriodicalId":338,"journal":{"name":"International Journal of Mass Spectrometry","volume":"508 ","pages":"Article 117371"},"PeriodicalIF":1.6000,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Mass Spectrometry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1387380624001829","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL","Score":null,"Total":0}
引用次数: 0
Abstract
We assess relativistic effects in the molecular hydration of late atomic transition metal cations (Groups 10–12) as revealed by a review of previously published experimental and theoretical hydration energies and by kinetic measurements at room temperature. To fill gaps in theoretical hydration energies, we report here newly computed hydration energies, with and without relativistic effects, for all 9 atomic transition metal ions in the three Groups using DFT and RI-MP2 theory. Rate coefficients are taken from previous work in our laboratory and we provide here, for the first time, the raw experimental data for the kinetics of all 9 hydration reactions. Trends in hydration energies and hydration kinetics are inspected and compared going down the Periodic Table. We find a strong 3rd-row enhancements in the hydration energy and the rate of hydration and these are attributed to relativistic contributions to the bonding of H2O to the 3rd-row transition metal cations. This behaviour is very much in line with that reported earlier with other molecular ligands.
期刊介绍:
The journal invites papers that advance the field of mass spectrometry by exploring fundamental aspects of ion processes using both the experimental and theoretical approaches, developing new instrumentation and experimental strategies for chemical analysis using mass spectrometry, developing new computational strategies for data interpretation and integration, reporting new applications of mass spectrometry and hyphenated techniques in biology, chemistry, geology, and physics.
Papers, in which standard mass spectrometry techniques are used for analysis will not be considered.
IJMS publishes full-length articles, short communications, reviews, and feature articles including young scientist features.