Infrared spectroscopic studies on photolysis of methyl iodide and its clusters in solid parahydrogen

Momose, Takamasa; Miki, Masaaki; Uchida, M.; Shioiri, Takayuki; Yoshizawa, Isamu; Shida, Tadamasa

doi:10.1063/1.469763

Cited by 75 publications

(67 citation statements)

References 36 publications

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“…[2][3][4][5] Concerning other molecules embedded in solid p-H 2 , HCl, 6 H 2 O, 7 CH 3 F, 8,9 CH 3 OH, 10 and recently CO ͑Ref. 11͒ have been reported.…”

Section: Introductionmentioning

confidence: 96%

Spectral line shape profile of rovibrational transitions of CO embedded in p-H2 crystals studied by high resolution IR diode laser spectroscopy

Toda¹,

Mizoguchi²,

Kanamori³

2010

The Journal of Chemical Physics

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Line profiles of rovibrational transitions of CO embedded in p-H(2) crystals were studied by high resolution midinfrared diode laser spectroscopy. The line profile analysis for the R(0)(parallel), R(0)(perpendicular), P(1)(parallel), and P(1)(perpendicular) transitions shows that spectral line shapes are well reproduced by a convolution of Gaussian and Lorentzian functions. The temperature dependence of the Lorentzian Gamma(L)(T) and Gaussian widths Gamma(G)(T) shows that there is a nonzero linewidth contribution to each at the T = 0 K limit. The main part of the Lorentzian width Gamma(L)(T = 0) shows anisotropy in the hcp structure and is explained by spontaneous decay of the rotational excited state energy to phonon modes. A smaller part of Gamma(L)(T = 0) is attributed to inhomogeneous broadening due to the point defects of other CO molecules in the crystal. On the other hand, the Gaussian width Gamma(G)(T = 0) is explained by inhomogeneous broadening due to dislocations. In the T > 0 region, Gamma(L)(T) shows strong temperature dependence but Gamma(G)(T) does not. The center frequencies of the R(0)(perpendicular) and P(1)(parallel) transitions show blueshifts and those of the R(0)(parallel) and P(1)(perpendicular) transitions show redshifts with increasing temperature. This phenomenon is explained by a decrease in the anisotropy in the crystal field, which is caused by the averaging of thermal lattice fluctuations. Furthermore, the contribution of vibration and rotation to the linewidth is discussed.

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“…[2][3][4][5] Concerning other molecules embedded in solid p-H 2 , HCl, 6 H 2 O, 7 CH 3 F, 8,9 CH 3 OH, 10 and recently CO ͑Ref. 11͒ have been reported.…”

Section: Introductionmentioning

confidence: 96%

Spectral line shape profile of rovibrational transitions of CO embedded in p-H2 crystals studied by high resolution IR diode laser spectroscopy

Toda¹,

Mizoguchi²,

Kanamori³

2010

The Journal of Chemical Physics

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“…As a consequence, photoproducts such as C atom and CH 3 radical produced on ultraviolet (UV) irradiation of C 2 (Ref. 31) and CH 3 I, [32][33][34] respectively, become excellent sources for studying bimolecular reactions in solid p-H 2 . We have employed this method to investigate the reactions of C or CH 3 with several small molecules in solid p-H 2 .…”

Section: Introductionmentioning

confidence: 99%

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

Bahou

Tanaka

et al. 2012

The Journal of Chemical Physics

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The reactions of chlorine and hydrogen atoms with trans-1,3-butadiene in solid para-hydrogen (p-H(2)) were investigated with infrared (IR) absorption spectra. When a p-H(2) matrix containing Cl(2) and trans-1,3-butadiene was irradiated with ultraviolet light at 365 nm, intense lines at 650.3, 809.0, 962.2, 1240.6 cm(-1), and several weaker ones due to the trans-1-chloromethylallyl radical, ●(CH(2)CHCH)CH(2)Cl, appeared. Observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++g(2d, 2p) method. That the Cl atom adds primarily to the terminal carbon atom of trans-1,3-butadiene is in agreement with the path of minimum energy predicted theoretically, but in contrast to the reaction of Cl + propene in solid p-H(2) [J. Amicangelo and Y.-P. Lee, J. Phys. Chem. Lett. 1, 2956 (2010)] in which the addition of Cl to the central C atom is favored, likely through steric effects in a p-H(2) matrix. A second set of lines, intense at 781.6, 957.9, 1433.6, 2968.8, 3023.5, 3107.3 cm(-1), were observed when the UV-irradiated Cl(2)/trans-1,3-butadiene/p-H(2) matrix was further irradiated with IR light from a SiC source. These lines are assigned to the trans-1-methylallyl radical, ●(CH(2)CHCH)CH(3), produced from reaction of 1,3-butadiene with a H atom resulted from the reaction of Cl atoms with solid p-H(2) exposed to IR radiation.

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“…Although few in comparison to studies in Rg, MIS studies of stable molecules in SMH date back at least 25 years, 8 and photolysis of molecules trapped in SMH 9 has recently been employed to produce molecular radical species trapped in SMH. 10 Thus, a variety of spectroscopically and chemically interesting dopants show sufficient chemical compatibility to be trapped in SMH.…”

Section: Solid Molecular Hydrogens As Matrix Hostsmentioning

confidence: 99%

Ortho/para hydrogen converter for rapid deposition matrix isolation spectroscopy

Tam

Fajardo

1999

Review of Scientific Instruments

126

109

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We describe the construction and operation of a catalyst-bed type device for precooling and equilibrating the ortho/para composition of a hydrogen gas flow. We use this device to vapor deposit millimeters thick cryogenic parahydrogen (pH2) solids which are remarkably transparent [M. E. Fajardo and S. Tam, J. Chem. Phys. 108, 4237 (1998)]. Infrared absorption spectra of solids deposited at pH2 flow rates up to 290 mmol/h (solid thickness growth rates up to 75 μm/min indicate a residual orthohydrogen (oH2) content of less than 0.01%. Gas phase thermal conductivity measurements indicate a residual oH2 content of 0(−0+5)% for flow rates up to 1.9 mol/h. These pH2 solids can be doped readily by simple codeposition of various impurities produced by any of the numerous dopant sources developed in previous matrix isolation spectroscopy (MIS) studies. The long achievable path lengths, and the desirable properties of pH2 as a matrix host, will enable significant new fundamental and practical applications for MIS.

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Infrared spectroscopic studies on photolysis of methyl iodide and its clusters in solid parahydrogen

Cited by 75 publications

References 36 publications

Spectral line shape profile of rovibrational transitions of CO embedded in p-H2 crystals studied by high resolution IR diode laser spectroscopy

Spectral line shape profile of rovibrational transitions of CO embedded in p-H2 crystals studied by high resolution IR diode laser spectroscopy

Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and Cℓ2 in solid para-hydrogen

Ortho/para hydrogen converter for rapid deposition matrix isolation spectroscopy

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