Characterization of iso-CF2I2 in frequency and ultrafast time domains
被引:23
作者:
El-Khoury, Patrick Z.
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机构:
Bowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
Bowling Green State Univ, Ctr Photochem Sci, Bowling Green, OH 43403 USABowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
El-Khoury, Patrick Z.
[1
,2
]
George, Lisa
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机构:
Marquette Univ, Dept Chem, Milwaukee, WI 53201 USABowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
George, Lisa
[3
]
Kalume, Aimable
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h-index: 0
机构:
Marquette Univ, Dept Chem, Milwaukee, WI 53201 USABowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
Kalume, Aimable
[3
]
Reid, Scott A.
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机构:
Marquette Univ, Dept Chem, Milwaukee, WI 53201 USABowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
Reid, Scott A.
[3
]
Ault, Bruce S.
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机构:
Univ Cincinnati, Dept Chem, Cincinnati, OH 45221 USABowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
Ault, Bruce S.
[4
]
Tarnovsky, Alexander N.
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机构:
Bowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
Bowling Green State Univ, Ctr Photochem Sci, Bowling Green, OH 43403 USABowling Green State Univ, Dept Chem, Bowling Green, OH 43403 USA
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
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.
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Univ Chinese Acad Sci, Beijing 100049, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Lin, Dan
Hu, Lili
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机构:
Chinese Acad Sci, Inst Phys, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Hu, Lili
Liu, Sheng
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h-index: 0
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Univ Chinese Acad Sci, Beijing 100049, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Liu, Sheng
Qi, Wenke
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h-index: 0
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Univ Chinese Acad Sci, Beijing 100049, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Qi, Wenke
Cheng, Min
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机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Chinese Acad Sci, Inst Chem, State Key Lab Mol React, Zhongguancun North First St 2, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Cheng, Min
Du, Yikui
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机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Du, Yikui
Zhu, Qihe
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机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Univ Chinese Acad Sci, Beijing 100049, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Lin, Dan
Hu, Lili
论文数: 0引用数: 0
h-index: 0
机构:
Chinese Acad Sci, Inst Phys, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Hu, Lili
Liu, Sheng
论文数: 0引用数: 0
h-index: 0
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Univ Chinese Acad Sci, Beijing 100049, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Liu, Sheng
Qi, Wenke
论文数: 0引用数: 0
h-index: 0
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Univ Chinese Acad Sci, Beijing 100049, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Qi, Wenke
Cheng, Min
论文数: 0引用数: 0
h-index: 0
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Chinese Acad Sci, Inst Chem, State Key Lab Mol React, Zhongguancun North First St 2, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Cheng, Min
Du, Yikui
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h-index: 0
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China
Du, Yikui
Zhu, Qihe
论文数: 0引用数: 0
h-index: 0
机构:
Chinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R ChinaChinese Acad Sci, Beijing Natl Lab Mol Sci, State Key Lab Mol React Dynam, Inst Chem, Beijing 100190, Peoples R China