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Ti2:从基质共振拉曼光谱精确测定解离能以及与稀有气体的化学相互作用。

Ti2: accurate determination of the dissociation energy from matrix resonance Raman spectra and chemical interaction with noble gases.

作者信息

Himmel Hans-Jörg, Bihlmeier Angela

机构信息

Institut für Anorganische Chemie, Universität Karlsruhe, Engesserstrasse, Geb. 30.45, 76180 Karlsruhe, Germany.

出版信息

Chemistry. 2004 Feb 6;10(3):627-33. doi: 10.1002/chem.200305382.

Abstract

UV-visible and resonance Raman spectra of Ti(2) isolated in Ar, Kr, and Xe matrices at temperatures of 10 K were measured by using the 514 nm line of an Ar ion laser. The data show that the Ti(2) molecule interacts strongly with Xe, leading to a significant weakening of the Ti[bond]Ti bond strength. The f(Ti[bond]Ti) force constant decreases in the series Ar>Kr>Xe, from 232.8 Nm(-1) in Ar and 225.5 Nm(-1) in Kr to 199.7 Nm(-1) in Xe. Additional experiments in an Ar matrix containing 2 % of Xe indicate the formation of a molecule of the formula Ti(2)Xe. Our spectra for Ti(2) in an Ar matrix give evidence for several previously not observed members of the Stokes progression. The sum of experimental data allows for an improved estimation of the dissociation energy on the basis of a LeRoy-Bernstein-Lam analysis. A dissociation energy of 1.18 eV was derived from this analysis. The UV-visible data give evidence of the vibrational levels of an excited state of Ti(2).

摘要

利用氩离子激光器的514 nm谱线,测量了在10 K温度下,Ti₂在氩、氪和氙基质中分离时的紫外可见光谱和共振拉曼光谱。数据表明,Ti₂分子与氙强烈相互作用,导致Ti—Ti键强度显著减弱。f(Ti—Ti)力常数在Ar>Kr>Xe系列中降低,从氩中的232.8 Nm⁻¹、氪中的225.5 Nm⁻¹降至氙中的199.7 Nm⁻¹。在含有2%氙的氩基质中进行的额外实验表明,形成了化学式为Ti₂Xe的分子。我们在氩基质中对Ti₂的光谱为斯托克斯级数中几个以前未观察到的成员提供了证据。实验数据的总和使得基于勒罗伊 - 伯恩斯坦 - 拉姆分析对离解能进行改进估计成为可能。通过该分析得出离解能为1.18 eV。紫外可见数据证明了Ti₂激发态的振动能级。

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