Infrared Matrix-isolation Study of New Noble-gas Compounds Cheng Zhu Department of Chemistry, University of Helsinki 20.06.2016

Content 1. Introduction 2. Results 3. Results in brief 2.1. Noble-gas hydrides: HKrCCCl and HXeCCCl 2.2. Fluorinated noble-gas cyanides: FKrCN, FXeCN, and FXeNC 3. Results in brief

1. Introduction

Reactivity of xenon is not trivial. 1. Introduction Reactivity of xenon is not trivial.

1. Introduction Neil Bartlett: 1962 Xenon hexafluoroplatinate PtF6 Neil Bartlett: 1962 Xenon hexafluoroplatinate Xe+[PtF6]− Paul R. Fields: 1962 RnF2

1. Introduction 1963 Crystals of KrF4 FKrF 1963 FKrF in an Ar matrix A.V. Grosse, A.D. Kirshenbaum, A.G. Streng, L.V. Streng, Science 139, 1047 (1963) 1963 FKrF in an Ar matrix J.J. Turner, G.C. Pimentel, Science 140, 974 (1963) FKrCCH in a Kr matrix L. Khriachtchev, A. Domanskaya, J. Lundell, A. Akimov, M. Räsänen, and E. Misochko, J. Phys. Chem. A 114, 4181 (2010).

1. Introduction Others ? 1963 KrF2 1962 Xe+[PtF6]− 1962 RnF2

1. Introduction 2000: The first neutral argon Compound: HArF L. Khriachtchev, M. Pettersson, N. Runeberg, J. Lundell, and M. Räsänen, Nature 406, 874 (2000).

1. Introduction 1995: Noble-gas hydrides Formula: HNgY University of Helsinki where Ng = Noble-gas atom Y = Electronegative atom or fragment Examples: HXeI, HKrCl, and HArF Charge transfer (HNg)+Y- Very intense H‒Ng stretching mode Can be easily monitored by IR spectroscopy

Experimental procedure 1. Introduction Experimental procedure FTIR spectrometer Computer Detector H + Ng + Y HY + Ng HNgY IR Temperature controller Evacuated sample cell Cold window Needle valve HY/Ng 1/1000 UV light

Formation of HKrCCCl in a Kr matrix 2. Results 2.1. New noble-gas hydrides (HNgY) Formation of HKrCCCl in a Kr matrix Depositition and photolysis by UV light HCCCl + Kr H + Kr + CCCl h1 Annealing H + Kr + CCCl HKrCCCl  Decomposition by UV light HKrCCCl H + Kr + CCCl h2 C. Zhu, M. Räsänen, and L. Khriachtchev, J. Chem. Phys. 143, 244319 (2015).

Calculated and experimental frequencies of HKrCCCl and HXeCCCl 2. Results 2.1. New noble-gas hydrides (HNgY) 2.1 Noble-gas compound (HNgY) Calculated and experimental frequencies of HKrCCCl and HXeCCCl   Calculated frequencies, cm-1 Experimental HKrCCCl 1421.8 1306 and 1315 2122.7 2070.7 HXeCCCl 1633.0 1500, 1550, and 1569 2122.1 2077.4 The calculations are performed at the CCSD(T)/def2-TZVPPD level of theory.

Formation of FKrCN in a Kr matrix 2. Results 2.2. Fluorinated noble-gas cyanides (YNgY’) Formation of FKrCN in a Kr matrix Deposition and photolysis by UV light FKrCN formed (3 K) Annealing at 25 K F + Kr + CN FKrCN  Decompostion by UV light FKrCN F + Kr + CN h C. Zhu, M. Räsänen, and L. Khriachtchev, J. Chem. Phys. 143, 074306 (2015)

Calculated and experimental frequencies of 2. Results 2.2. Fluorinated noble-gas cyanides (YNgY’) 2.2 Noble-gas compound (YNgY’) Calculated and experimental frequencies of FKrCN, FXeCN, and FXeNC   Calculated frequencies, cm-1 Experimental FKrCN 357.4 357 505.8 505 2185.3 2158 FXeCN 384.0 366 496.1 487 2191.8 2159 FXeNC 397.1 - 524.4 517 2069.4 2041 The calculations are performed at the CCSD(T)/def2-TZVPPD level of theory.

3. Results in brief Two new noble-gas hydrides are synthesized: HKrCCCl and HXeCCCl Three fluorinated noble-gas cyanides are synthesized: FKrCN, FXeCN, and FXeNC

Thank you!