Infrared studies of the nitrous acid complexes with Xe and N2 in argon, krypton and xenon matrices

Mielke, Zofia; Talik, Tadeusz; Tokhadze, K. G.

doi:10.1016/s0022-2860(98)00906-5

Cited by 16 publications

(13 citation statements)

References 20 publications

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“…As shown in Table 3, interestingly, the gas phase calculations show that the TiH 2 scissor and wag frequencies are nearly degenerate (612.4 vs. 613.9 cm -1 ) while the argon matrix calculations indicate that the two frequencies are just like a doublet (594.1 vs. 600.1 cm -1 ). This point should be paid more attention to during the assignment of the experimental frequencies since the doublets may be easily explained to be due to the matrix site effect [4,9,10,34]. Note that the experimental argon matrix frequency 588.5 cm -1 was only assigned to the TiH 2 wag mode of their calculation (616.8 cm -1 ) [3].…”

Section: Resultsmentioning

confidence: 98%

“…However, the existing calculations are not in exact consistency with the experiments because the experimental frequencies were measured from the R 2 MH 2 molecules isolated in the rare gas matrix while the calculations were based on a gas phase model and the matrix effect was not modelled. Existing experiments have demonstrated that the rare gas matrix has an evident effect on the infrared fundamental frequencies of a single molecule [7][8][9] and that, sometimes, the matrix effect can even change the relative magnitude of two vibrational frequencies [9,10]. As a consequence, the modelling of the rare gas matrix effect should be of great significance for understanding the experimental matrix isolation infrared spectra of the R 2 MH 2 molecules.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Liu

Zhao

2008

Struct Chem

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Using Stuttgart/Dresden effective core potentials MWB28, MWB60, and GTO valence basis sets (8s7p6d)/[6s5p3d], (8s7p6d)/[6s5p3d] for Zr and Hf atoms and 6-311++G(3df,3pd) basis set for C, H, O, and Ti atoms, tight convergence criteria geometry optimizations and harmonic frequency calculations are performed at B3LYP and B3LYP/IEF-PCM levels of theory so as to model the gas phase and argon matrix infrared spectra of the tetrahedral molecules R 2 MH 2 (R = D(H), CH 3 , OH; M = Ti, Zr, Hf). Influence of the transition metal and/or substituent group on the symmetric and asymmetric stretching frequencies of the MH 2 fragment of the R 2 MH 2 molecules is investigated at both the levels of theory. The modelling of the argon matrix effect improves the agreement between the calculated frequencies and the experimental ones. The calculated argon matrix to gas phase frequency shifts is compared reasonably to the experimental argon to neon matrix shifts.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Liu

Zhao

2008

Struct Chem

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“…However, the experimental measurements were conducted in solid matrices while the theoretical calculations were based on gas phase model. As we know, the solid matrix has an unneglectable effect on the infrared frequencies of both the monomers and the complexes [12, [26][27][28]. It's possible that, based on gasphase calculations, the frequencies of some vibrations of a complex are blue-shifted with respect to those of its monomers while, based on experimental matrix infrared spectra, the former become red-shifted with respect to the latter instead!…”

Section: Resultsmentioning

confidence: 99%

Searching blue-shifted O–H···Y hydrogen bond in CH3OH complexes with CF4, C2F2, OC, Ne, and He: a theoretical study

Liu

2007

Struct Chem

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The hydrogen-bonded structures of the CH 3 OH complexes with CF 4 , C 2 F 2 , OC, Ne, and He are designated as the starting points for geometry optimizations without and with counterpoise (CP) correction at MP2 level of theory with the basis sets 6-31+G*, 6-31++G**, and 6-311++G**, respectively. Tight convergence criteria are applied throughout all geometry optimizations in order to reduce the computational errors. According to the optimizations without CP correction, a blue-shifted O-HÁÁÁY (where Y = F, O, Ne, or He) hydrogen bond exists in all these five complexes. The magnitudes of blue shifts of m(O-H) of the former four complexes with respect to that of CH 3 OH are reduced greatly when the polarization and diffuse functions of the hydrogen atoms are added (results from 6-31+G* versus those from 6-31++G**). However, for the complexes CH 3 OH-CF 4 and CH 3 OH-C 2 F 2 , our optimizations using the CP corrections did not find the hydrogen-bonded structure to be a stationary point. The energy minimum of both the complexes corresponds to a non-hydrogen-bonded structure.

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“…Both are spectroscopically dark but possibly responsible for additional matrix inhomogeneities. 48 Albeit the good qualitative agreement between MD simulation and experiment, what the partial decay of the anisotropy of trans-HONO is concerned, the overall times cales are completely wrong. Two possible reasons for this discrepancy come into ones mind:…”

Section: Discussionmentioning

confidence: 97%

Rotational dynamics of nitrous acid (HONO) in Kr matrix

Botan

Hamm

2008

The Journal of Chemical Physics

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With the help of ultrafast time-resolved infrared spectroscopy, we investigate rotational diffusion of cisand trans-nitrous acid (HONO) in solid Kr at 30 K, as well as its reorientation upon the IR-driven cis -> trans isomerization. We find different mobilities for the two isomers: cis-HONO is pinned to the matrix with no decay of the anisotropy on the 100 ns time scale, whereas trans-HONO rotates around its long axis, reducing its anisotropy partially on that time scale. The long axis itself, defined by the terminal oxygen and hydrogen atoms of HONO, stays fixed on even a minute time scale. Accompanying molecular dynamics simulations reproduce the anisotropic rotational diffusion of trans-HONO correctly, although on a completely wrong time scale, whereas they would predict complete reorientation of cis-HONO within approximate to 10 ps, in harsh disagreement with the experiment. We attribute the mismatch of orientational time scales to either too soft interaction potentials or to the fact that HONO occupies an interstitial rather than a monosubstitutional matrix site. The experiments furthermore show that the direction of the OH bond hardly changes during the IR-driven cis -> trans isomerization, in contrast to the intuitive picture that it is mostly the light hydrogen which moves. Rather, it is the two central nitrogen and oxygen atoms that are removed during isomerization in a hula hoop fashion, whereas the terminal atoms are still pinned to the matrix cage. With the help of ultrafast time-resolved infrared spectroscopy, we investigate rotational diffusion of cis-and trans-nitrous acid ͑HONO͒ in solid Kr at 30 K, as well as its reorientation upon the IR-driven cis → trans isomerization. We find different mobilities for the two isomers: cis-HONO is pinned to the matrix with no decay of the anisotropy on the 100 ns time scale, whereas trans-HONO rotates around its long axis, reducing its anisotropy partially on that time scale. The long axis itself, defined by the terminal oxygen and hydrogen atoms of HONO, stays fixed on even a minute time scale. Accompanying molecular dynamics simulations reproduce the anisotropic rotational diffusion of trans-HONO correctly, although on a completely wrong time scale, whereas they would predict complete reorientation of cis-HONO within Ϸ10 ps, in harsh disagreement with the experiment. We attribute the mismatch of orientational time scales to either too soft interaction potentials or to the fact that HONO occupies an interstitial rather than a monosubstitutional matrix site. The experiments furthermore show that the direction of the OH bond hardly changes during the IR-driven cis → trans isomerization, in contrast to the intuitive picture that it is mostly the light hydrogen which moves. Rather, it is the two central nitrogen and oxygen atoms that are removed during isomerization in a hula hoop fashion, whereas the terminal atoms are still pinned to the matrix cage. Rotational dynamics of nitrous acid "HONO… in Kr matrix

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Infrared studies of the nitrous acid complexes with Xe and N2 in argon, krypton and xenon matrices

Cited by 16 publications

References 20 publications

Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Searching blue-shifted O–H···Y hydrogen bond in CH3OH complexes with CF4, C2F2, OC, Ne, and He: a theoretical study

Rotational dynamics of nitrous acid (HONO) in Kr matrix

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