Characterization of iso-CF2I2 in frequency and ultrafast time domains

被引:23
作者
El-Khoury, Patrick Z. [1 ,2 ]
George, Lisa [3 ]
Kalume, Aimable [3 ]
Reid, Scott A. [3 ]
Ault, Bruce S. [4 ]
Tarnovsky, Alexander N. [1 ,2 ]
机构
[1] Bowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
[2] Bowling Green State Univ, Ctr Photochem Sci, Bowling Green, OH 43403 USA
[3] Marquette Univ, Dept Chem, Milwaukee, WI 53201 USA
[4] Univ Cincinnati, Dept Chem, Cincinnati, OH 45221 USA
基金
美国国家科学基金会;
关键词
ab initio calculations; bonds (chemical); ground states; infrared spectra; matrix isolation spectra; metastable states; molecule-photon collisions; organic compounds; photodissociation; photolysis; potential energy surfaces; time resolved spectra; RESONANCE RAMAN OBSERVATION; DENSITY-FUNCTIONAL THEORY; DIRECT PHOTODISSOCIATION REACTION; VIBRATIONAL-ENERGY TRANSFER; A-BAND PHOTODISSOCIATION; X-RAY-DIFFRACTION; ULTRAVIOLET PHOTOLYSIS; PHOTOISOMERIZATION REACTION; CYCLOPROPANATION REACTIONS; POLYATOMIC-MOLECULES;
D O I
10.1063/1.3357728
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The photolysis of diiododifluoromethane (CF2I2) in condensed phases was studied by a combination of matrix isolation and ultrafast time-resolved spectroscopy, in concert with ab initio calculations. Photolysis at wavelengths of 355 or 266 nm of CF2I2:Ar samples (1:5000) held at similar to 8 K yielded iso-CF2I2 (F2C-I-I), a metastable isomer of CF2I2, characterized here for the first time. The infrared (IR) spectra of this isomer were recorded in matrix experiments, and the derived positions of the C-F stretching modes are in very good agreement with the predictions of high level ab initio calculations, which show that the iso-form is a minimum on the CF2I2 ground state potential energy surface. The formation of this isomer following 350 nm excitation of CF2I2 in room temperature CCl4 solutions was monitored through its intense C-F stretching mode by means of ultrafast time-resolved IR absorption. Together, matrix isolation and ultrafast IR absorption experiments suggest that the formation of iso-CF2I2 occurs via recombination of CF2I radical and I atom. Ultrafast IR experiments detect a delayed rise of iso-CF2I-I absorption, placing an upper limit of 400 fs for the C-I bond dissociation and primary geminate recombination processes. The product absorption spectrum recorded 1 ns after 350 nm excitation of CF2I2 in solution is virtually identical to the visible absorption spectrum of iso-CF2I2 trapped in matrix isolation experiments [with subtracted I-2(X) absorption]. The formation of this isomer in solution at room temperature has direct dynamic implications for the ultrafast production of molecular iodine from electronically excited CF2I2.
引用
收藏
页数:11
相关论文
共 50 条
  • [31] 2D heterodyne-detected sum frequency generation study on the ultrafast vibrational dynamics of H2O and HOD water at charged interfaces
    Inoue, Ken-ichi
    Nihonyanagi, Satoshi
    Singh, Prashant C.
    Yamaguchi, Shoichi
    Tahara, Tahei
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2015, 142 (21)
  • [32] Characterization of N+n=2-18 clusters produced by 252Cf fission fragment impact on a N2 ice target
    Fernandez-Lima, F. A.
    Ponciano, C. R.
    Faraudo, G. S.
    Grivet, M.
    da Silveira, E. F.
    Nascimento, M. A. Chaer
    [J]. CHEMICAL PHYSICS, 2007, 340 (1-3) : 127 - 133
  • [33] Resolved (v1, v2=1) Combination Vibrational States of CF3 Fragments in the Photofragment Translational Spectra of CF3I
    Lin, Dan
    Hu, Lili
    Liu, Sheng
    Qi, Wenke
    Cheng, Min
    Du, Yikui
    Zhu, Qihe
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2016, 120 (49) : 9682 - 9689
  • [34] The spectroscopic characterization of the methoxy radical. I. Rotationally resolved A 2A1-X 2E electronic spectra of CH3O
    Liu, Jinjun
    Chen, Ming-Wei
    Melnik, Dmitry
    Yi, John T.
    Miller, Terry A.
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2009, 130 (07)
  • [35] Pressure Dependence of Iso-Propyl Nitrate Formation in the i-C3H7O2 + NO Reaction
    Butkovskaya, N. I.
    Kukui, A.
    Le Bras, G.
    [J]. ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS, 2010, 224 (7-8): : 1025 - 1038
  • [36] Structure and dynamic behavior of CF3CO2- in solution with a previously unknown η2 chelation mode to silver(I) in [Ag2(2-NCH2C6H5NCTPP)2]2+•[Ag2(O2CCF3)4]2-
    Hsaio, De-Zhi
    Chen, Jyh-Horung
    Wang, Shin-Shin
    Tung, Jo-Yu
    [J]. POLYHEDRON, 2011, 30 (17) : 2908 - 2913
  • [37] Direct observation of ferroelectric domains created by Wigner crystallization of electrons in α-[bis(ethylenedithio)tetrathiafulvalene]2I3
    Yamamoto, Kaoru
    Kowalska, Aneta Aniela
    Yakushi, Kyuya
    [J]. APPLIED PHYSICS LETTERS, 2010, 96 (12)
  • [38] Chlorodifluorothioacetic acid, CF2CIC(O)SH:: Synthesis, characterization, X-ray structure and conformational properties
    Erben, Mauricio F.
    Boese, Roland
    Willner, Helge
    Della Vedovaja, Carlos O.
    [J]. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2007, 2007 (29) : 4917 - 4926
  • [39] Time-frequency resolved coherent Raman scattering from molecular liquids and their mixtures with quasi-cw noisy light:: I(2)CRS spectrograms
    Ulness, DJ
    Stimson, MJ
    Kirkwood, JC
    Albrecht, AC
    [J]. LASER CHEMISTRY, 1999, 19 (1-4) : 11 - 18
  • [40] OXIDATION OF PALLADIUM(I) DIMERS - FORMATION AND X-RAY CRYSTAL-STRUCTURE OF [(ME(3)P)(2)PD(MU-OH)(2)PD(PME(3))(2)](CF3SO3)(2)
    PIERI, G
    PASQUALI, M
    LEONI, P
    ENGLERT, U
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1995, 491 (1-2) : 27 - 30