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1.
J Phys Chem A ; 123(35): 7590-7596, 2019 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-31390209

RESUMO

In this paper, we describe amplified spontaneous emission (ASE) from the f' 0g+ (1D2) ion-pair state of I2 populated through a two-step laser excitation technique via the B 3Π(0u+) valence state. The intense infrared emission propagating in the direction of the incident laser beam is assigned to the ASE transition from the f' 0g+ (1D2) state to the F' 0u+ (1D2) ion-pair state. The subsequent ultraviolet fluorescence transition from the F' 0u+ (1D2) state to the 0g+ (bb) state as well as the 0g+ (ab) state is also reported. By Franck-Condon simulation of the cascading F' 0u+ (1D2) → 0g+ (bb) band, we determine the population distributions in the F' 0u+ (1D2) state generated by ASE, which are consistent with the intensity profile of the mid-infrared ASE spectrum. Finally, employing these vibrational distributions for the F' 0u+ (1D2) state, spectral parameters for the shallow 0g+ (ab) state are derived.

2.
J Chem Phys ; 145(12): 124304, 2016 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-27782632

RESUMO

We have generated SiCN in a supersonic free expansion, and measured the laser induced fluorescence (LIF) spectrum. Prior to the experiments, ab initio calculations were carried out to obtain the information necessary for searching for the LIF signals. In addition to the X̃ 2Π state, the optimized structures of three excited states, 2Δ, 2Σ+, and 2Σ-, have been obtained. Guided by the predictions, the LIF excitation spectrum of SiCN was observed in the UV region. The rotational structure of the 000 band with the origin, 29 261.639 cm-1, indicated that the electronic transition is à 2Δ-X̃ 2Π. The spin-orbit (SO) constants of the X̃ 2Π and à 2Δ states were determined to be 140.824 and 4.944 cm-1, respectively. In the à 2Δ state, the Fermi resonance between the (0, 20, 0) 2Δ and (0, 00, 1) 2Δ vibronic levels was identified. The molecular constants of the X̃ 2Π state were determined through the simultaneous analysis of the combination differences derived from the present LIF data with the previously reported rotational transitions. The spectroscopic parameters of the à 2Δ state were also obtained from the analysis where the constants of the X̃ 2Π state, derived above, were fixed at those values.

3.
Phys Chem Chem Phys ; 18(28): 19464-71, 2016 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-27410159

RESUMO

We report the observation of amplified spontaneous emission for the first time from the 0 ((3)P0) and 0 ((1)D2) ion-pair states of Br2 by using an optical-optical double resonance technique through the B (3)Π(0) valence state as the intermediate state. The strong infrared emission propagating along the incident laser radiation is assigned to the parallel ASE transitions from the 0 ion-pair states down to the nearby 0 ion-pair states. The subsequent UV fluorescence from the 0 states to the high vibrational levels of the ground state is also observed. By the Franck-Condon simulation of the cascade UV fluorescence, we determine the vibrational distributions in the 0 states populated by ASE, which are consistent with the intensity distribution in the dispersed infrared ASE spectrum. The lifetimes of the relevant ion-pair states are evaluated by analyzing the temporal profiles of the UV fluorescence.

4.
Phys Chem Chem Phys ; 18(21): 14292-8, 2016 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-27165483

RESUMO

We report the first observation of collision induced state-to-state energy transfer from the 2u ((1)D2) (v2u = 3-7) ion-pair state of I2 using a perturbation facilitated optical-optical double resonance technique through the c (1)Πg∼ B (3)Π(0) hyperfine mixed double-faced valence state as the intermediate state. The excitation of the 2u ((1)D2) state yielded the weak UV fluorescence from the wide range of vibrational levels in the nearby 2g ((1)D2) state. The vibrational distribution in the 2g ((1)D2) state derived by the Franck-Condon simulation of the UV fluorescence showed that the population in the 2u ((1)D2) state transfers mostly to the 2g ((1)D2) vibronic levels which are located energetically above the laser-prepared level. The radiative lifetimes and the self-quenching rate constants were determined to be 21.3 ± 0.1 and 44.6 ± 0.8 ns, and (1.30 ± 0.01) × 10(-9) and (2.26 ± 0.17) × 10(-9) cm(3) molecule(-1) s(-1) for the 2u ((1)D2) (v2u = 3) and 2g ((1)D2) (v2g = 5) states, respectively. The rate constant for the 2u ((1)D2) - 2g ((1)D2) collision induced state-to-state energy transfer was also evaluated to be (1.89 ± 0.01), (3.07 ± 0.07), and (3.77 ± 0.05) × 10(-10) cm(3) molecule(-1) s(-1) for the v2u = 3, 5, and 7 levels, respectively. The very large self-quenching cross sections for the ion-pair states of I2 could be explained by the harpoon mechanism.

5.
J Chem Phys ; 144(3): 034302, 2016 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-26801029

RESUMO

We report the spectroscopic and temporal analyses on the amplified spontaneous emission (ASE) from the single rovibrational levels of the Ω = 1u ion-pair series, γ 1u ((3)P2), H 1u ((3)P1), and 1u ((1)D2), of I2 by using a perturbation facilitated optical-optical double resonance technique through the c (1)Πg ∼ B (3)Π(0u (+)) hyperfine mixed valence state as the intermediate state. The ASE detected in the infrared region was assigned to the parallel transitions from the Ω = 1u ion-pair states down to the nearby Ω = 1g ion-pair states. The subsequent ultraviolet (UV) fluorescence from the Ω = 1g states was also observed and the relative vibrational populations in the Ω = 1g states were derived through the Franck-Condon simulation of the intensity pattern of the vibrational progression. In the temporal profiles of the UV fluorescence, an obvious delay in the onset of the fluorescence was recognized after the excitation laser pulse. These results revealed that ASE is a dominant energy relaxation process between the Ω = 1u and 1g ion-pair states of I2. Finally, the lifetimes of the relevant ion-pair states were evaluated by temporal analyses of the UV fluorescence. The propensity was found which was the longer lifetime in the upper level of the ASE transitions tends to give intense ASE.

6.
J Chem Phys ; 145(21): 214304, 2016 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-28799389

RESUMO

The laser induced fluorescence (LIF) spectrum of the à 2Δ - X̃ 2Π transition was obtained for SiCN generated by laser ablation under supersonic free jet expansion. The vibrational structures of the dispersed fluorescence (DF) spectra from single vibronic levels (SVL's) were analyzed with consideration of the Renner-Teller (R-T) interaction. Analysis of the pure bending (ν2) structure by a perturbation approach including R-T, anharmonicity, spin-orbit (SO), and Herzberg-Teller (H-T) interactions indicated considerably different spin splitting for the µ and κ levels of the X̃ 2Π state of SiCN, in contrast to identical spin splitting for general species derived from the perturbation approach, where µ and κ specify the lower and upper levels, respectively, separated by R-T. Further analysis of the vibrational structure including R-T, anharmonicity, SO, H-T, Fermi, and Sears interactions was carried out via a direct diagonalization procedure, where Sears resonance is a second-order interaction combined from SO and H-T interactions with Δ K = ± 1, ΔΣ = ∓1, and Δ P = 0, and where P is a quantum number, P = K + Σ. The later numerical analysis reproduced the observed structure, not only the pure ν2 structure but also the combination structure of the ν2 and the Si-CN stretching (ν3) modes. As an example, the analysis demonstrates Sears resonance between vibronic levels, (0110) κ Σ(+) and (0200)µΠ12, with Δ K = ± 1 and Δ P = 0. On the basis of coefficients of their eigen vectors derived from the numerical analysis, it is interpreted as an almost one-to-one mixing between the two levels. The mixing coefficients of the two vibronic levels agree with those obtained from computational studies. The numerical analysis also indicates that some of the vibronic levels show chaotic characteristics in view of the two-dimensional harmonic oscillator (2D-HO) basis which is used as the basis function in the present numerical analysis; i.e., the eigen vectors for some of the observed levels have several components of the basis, and we have not been able to give precise vibronic assignments for the levels, but just vibronically labeled, referring the largest component in their vectors. (To emphasize this situation, we do not use the word "assignment," but prefer to use "label" as the meaning of just "label," but not "assign," throughout this paper.) The latter shows that the vibronic labels of the levels are meaningless, and the P quantum number and the order of their eigen states in the P matrix block derived in the numerical analysis only characterize the vibronic levels. Comparing the constants obtained for all of the interactions with those of species showing Sears resonance and studied previously, it is found that none of them are strong, but are moderate. It is thus concluded that the chaotic appearance is not derived by any strong interaction, but is induced by complex and accidental proximities of the vibronic levels caused by the moderate interactions.

7.
J Chem Phys ; 142(11): 114302, 2015 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-25796244

RESUMO

Rotationally resolved high-resolution fluorescence excitation spectra of the 0-0 band of the B̃(2)E(')←X̃(2)A2(') transition of the (15)N substituted nitrate radical were observed for the first time, by crossing a jet-cooled molecular beam and a single-mode dye laser beam at right angles. Several thousand rotational lines were detected in the 15 080-15 103 cm(-1) region. We observed the Zeeman splitting of intense lines up to 360 G in order to obtain secure rotational assignment. Two, nine, and seven rotational line pairs with 0.0248 cm(-1) spacing were assigned to the transitions from the X̃(2)A2(') (υ″ = 0, k″ = 0, N″ = 1, J″ = 0.5 and 1.5) to the (2)E3/2(') (J' = 1.5), (2)E1/2(') (J' = 0.5), and (2)E1/2(') (J' = 1.5) levels, respectively, based on the ground state combination differences and the Zeeman splitting patterns. The observed spectrum was complicated due to the vibronic coupling between the bright B̃(2)E(') (υ = 0) state and surrounding dark vibronic states. Some series of rotational lines other than those from the X̃(2)A2(') (J = 0.5 and 1.5) levels were also assigned by the ground state combination differences and the observed Zeeman splitting. The rotational branch structures were identified, and the molecular constants of the B̃(2)E1/2(') (υ = 0) state were estimated by a deperturbed analysis to be T0 = 15 098.20(4) cm(-1), B = 0.4282(7) cm(-1), and DJ = 4 × 10(-4) cm(-1). In the observed region, both the (2)E1/2(') and (2)E3/2(') spin-orbit components were identified, and the spin-orbit interaction constant of the B̃(2)E(') (υ = 0) state was estimated to be -12 cm(-1) as the lower limit.

8.
J Chem Phys ; 141(18): 184307, 2014 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-25399147

RESUMO

Rotationally resolved high-resolution fluorescence excitation spectra of (14)NO3 radical have been observed for the 662 nm band, which is assigned as the 0-0 band of the B̃(2)E' ←X̃(2)A2' transition, by crossing a single-mode laser beam perpendicularly to a collimated molecular beam. More than 3000 rotational lines were detected in 15,070-15,145 cm(-1) region, but it is difficult to find the rotational line series. Remarkable rotational line pairs, whose interval is about 0.0246 cm(-1), were found in the observed spectrum. This interval is the same amount with the spin-rotation splitting of the X̃(2)A2' (υ = 0, k = 0, N = 1) level. From this interval and the observed Zeeman splitting up to 360 G, seven line pairs were assigned as the transitions to the (2)E'(3/2) (J' = 1.5) levels and 15 line pairs were assigned as the transitions to the (2)E'(1/2) (J' = 0.5) levels. From the rotational analysis, we recognized that the (2)E' state splits into (2)E'(3/2) and (2)E'(1/2) by the spin-orbit interaction and the effective spin-orbit interaction constant was roughly estimated as -21 cm(-1). From the number of the rotational line pairs, we concluded that the complicated rotational structure of this 662 nm band of (14)NO3 mainly owes to the vibronic interaction between the B̃(2)E' state and the dark Ã(2)E″ state through the a2″ symmetry vibrational mode.

9.
J Phys Chem A ; 117(50): 13732-42, 2013 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-24083401

RESUMO

High-resolution Fourier transform infrared spectra of the 15NO3 ν3+ν4 and ν3+ν4-ν4 bands were observed in the 1472 and 1112 cm(-1) regions. Compared with the case of 14N species, large effects of perturbations were recognized in many rotational levels of the 15NO3 ν3+ν4 state, and it was found that the ν2+2ν4 state is responsible for the perturbation. Although a direct Coriolis interaction (Δν2 = 1, Δν3(or Δν4)=1) is not present between these two vibrational levels, anharmonic terms including Φ344 and Φ444 mix ν3+ν4 and 3ν4, ν2+2ν4, and ν2+2ν4 mixes with ν2+ν4 to produce Coriolis interaction between ν3+ν4 and ν2+2ν4. An analysis gave the energy difference of 7.274 cm(-1) between two levels, and interaction parameters were determined. Similar perturbation analysis was applied for the 14N species, and the previous (p)P(N,K) assignment of the ν3+ν4 A'-ν4 E' band was changed for giving one A2' state. Spectral lines to another A1' state were not assigned because of weak intensity, which is explained by intensity anomaly through vibronic interaction, reflecting the transition moment of the B2E'-X2A2' electronic band.

10.
J Phys Chem A ; 117(39): 9435-43, 2013 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-23461463

RESUMO

We have generated SiCN in supersonic free jet expansions and observed the laser induced fluorescence (LIF) spectrum. In addition to the vibronic bands from the vibrationless level of the X̃ (2)Π state, the hot bands from the bending vibrational level, à (01(1)0) (2)Φ - X̃ (01(1)0) (2)Δ and à (01(1)0) (2)Π - X̃ (01(1)0) (2)Σ((-)), have been measured. The rotational energy levels were reasonably analyzed as those of the (2)K' - (2)K″ transitions, but their line intensities calculated from the Hönl-London factors derived in the intermediate case between Hund's case (a) and (b) could not reproduce the observed spectra. The Hönl-London factors derived in the (2)Λ' - (2)Λ″ ((2)Δ - (2)Π) transition reasonably reproduced the spectra. It indicates that coupling between the electronic orbital and vibrational angular momenta is weak in the SiCN (2)Δ - (2)Π system, and a basis set of |Λ v2 l Σ;J P MJ>, the so-called "l-basis", better describes the system than that of |Λ v2 K Σ;J P MJ>.

11.
J Chem Phys ; 135(12): 124311, 2011 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-21974526

RESUMO

We have generated MgNC in supersonic free jet expansions and observed the laser induced fluorescence (LIF) of the Ã(2)Π-X̃(2)Σ(+) transition. We measured the LIF dispersed spectra from the single vibronic levels of the Ã(2)Π electronic state of MgNC, following excitation of each ν(2) bending vibronic band observed, i.e., the κ series of the (0,v(2)('),0)-(0,0,0), v(2)(') = 0, 1, 2, 4, and 6 vibronic bands. In the vibrational structure in the dispersed fluorescence spectra measured, the long progression of the ν(2) bending mode in the X̃(2)Σ(+) state is identified, e.g., up to v(2)('')=14 in the (0,6,0)-(0,v(2)(''),0) spectrum. This enables us to derive the potential curve of the ν(2) bending mode in the X̃(2)Σ(+) state. We used two kinds of models to obtain the potential curve; (I) the customary formula expressed in the polynomial series of the (v(2)('')+(d(2)/2)) term and (II) the internal rotation model. The potential curve derived from model (I) indicates the convergence of the bending vibrational levels at about 800 cm(-1) from the vibrationless level of MgNC, which may correspond to the barrier height of the isomerization reaction, MgNC ⇌ MgCN, in the X̃(2)Σ(+) state. Model (II) gives a simple picture for the isomerization reaction pathway with a barrier height of about 630 cm(-1) from the vibrationless level of the more stable species, MgNC. This shows that the v(2)('')=8 bending vibrational level of MgNC is already contaminated by the v(2)('')=2 bending vibrational level of the isomer, MgCN, and implies that the isomerization reaction begins at the v(2) ('')=8 level. The bending potential surface and the isomerization reaction pathway, MgNC ⇌ MgCN, in the X̃(2)Σ(+) state are discussed by comparing the potential derived in this study with the surface obtained by quantum chemical calculation.

12.
J Phys Chem A ; 114(2): 980-6, 2010 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-20025259

RESUMO

We have observed the infrared spectrum of (15)NO(3) by a high resolution Fourier transform infrared (FT-IR) spectrometer using the reaction of F atoms with H(15)NO(3). Five (2)E'-(2)A(2)' bands are identified in the 1850-3150 cm(-1) region. The rotational analyses indicate that these bands have the lower state in common, which coincides with the ground state of planar D(3h) symmetry. The upper (2)E' states more or less suffer from perturbations by close-lying dark states. Among them, those of the 2004, 2128, and 2492 cm(-1) bands are analyzed to determine molecular parameters in these states by fixing the ground-state constants to those derived by a combination difference method. The spin-orbit and Coriolis coupling constants in the (2)E' states are substantially different for different vibronic states. The vibrational assignments of NO(3) in the ground electronic state are discussed using experimental data heretofore available, supplemented by those obtained by the present study.

13.
J Chem Phys ; 128(16): 164320, 2008 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-18447452

RESUMO

This paper reports the results of processes resulting in D0(u) (+)-X (1)Sigma(g) (+) emission when a single rovibrational level of the E0(g) (+) state is prepared. Our study reveals that two kinds of processes populate the D0(u) (+) state; which one occurs depends on the experimental conditions. One process involves amplified spontaneous emission from the E0(g) (+) state. The other is collision-induced energy transfer in self-quenching. We distinguish these two processes from the time profiles of fluorescence signals. These processes give completely different vibrational distributions in the D0(u) (+) state from a given rovibrational level of the E0(g) (+) state. The discrepancy between our results and previous results for the E0(g) (+)-->D0(u) (+) relaxation is briefly discussed.

14.
J Chem Phys ; 127(4): 044314, 2007 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-17672697

RESUMO

We have generated MgNC in supersonic free jet expansions and measured the laser induced fluorescence excitation spectra of the Mg-N-C bending vibronic bands of the A 2Pi-X 2Sigma+ transition. In addition to the two vibronic bands, 2(0) (1), kappa 2Sigma(+)- and 2(0) (2), kappa 2Pi-2Sigma+, reported previously, the 2(0) (2), mu 2Pi1/2-(2)Sigma+ vibronic subband was found just above the 2(0) (1) band. The most remarkable feature of this subband is unexpected rotational structure of the A (020) mu 2Pi1/2 level, showing the splitting of the e and f sublevels. On the basis of the fact that the A (020) mu 2Pi1/2 level lies very close to the A (010) kappa2Sigma+ level, the ef splitting is ascribed to P-type doubling which is induced by Coriolis interaction between these two bending vibronic levels. Introducing the Coriolis coupling terms arising from the G-uncoupling operator, -J+/-G22-/+, and the spin-Coriolis interaction, S+/-G22-/+, into the rotational Hamiltonian, this unexpected rotational structure has been analyzed. This P-type doubling would be one of the rare examples exhibiting the Coriolis interaction between two bending vibronic levels with Deltav2=+/-1 and Deltal=-/+1. Through the molecular constants of the A (010) kappa 2Sigma+, (020) kappa 2Pi, and mu 2Pi1/2 levels, the Renner-Teller vibronic structure of the nu2 bending mode in the A 2Pi state has been characterized. The observed vibronic bands analyzed in this study show some anomalies in the band intensities. Based on the information of the nu2 bending vibronic structure derived from the present analyses, we discuss the intensity anomalies.

15.
J Phys Chem A ; 111(17): 3342-8, 2007 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-17425290

RESUMO

The rate constant of the reaction of BrO with CH(3)O(2) was determined to be k1 = (6.2 +/- 2.5) x 10(-12) cm3 molecule(-1) s(-1) at 298 K and 100-200 Torr of O2 diluent. Quoted uncertainty was two standard deviations. No significant pressure dependence of the rate constants was observed at 100-200 Torr total pressure of N2 or O2 diluents. Temperature dependence of the rate constants was further investigated over the range 233-333 K, and an Arrhenius type expression was obtained for k1 = 4.6 x 10(-13) exp[(798 +/- 76)/T] cm3 molecule(-1) s(-1). The product branching ratios were evaluated and the atmospheric implications were discussed.


Assuntos
Compostos de Bromo/química , Gases/química , Óxidos/química , Peróxidos/química , Simulação por Computador , Radicais Livres/química , Cinética , Metilação , Temperatura
16.
J Phys Chem A ; 110(32): 9861-6, 2006 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-16898687

RESUMO

The reactions of iodine monoxide radical, IO, with alkyl peroxide radicals, RO(2) (R = CH(3), C(2)H(5), and CF(3)), have been studied using cavity ring-down spectroscopy. The rate constant of the reaction of IO with CH(3)O(2) was determined to be (7.0 +/- 3.0) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K and 100 Torr of N(2) diluent. The quoted uncertainty is two standard deviations. No significant pressure dependence of the rate constant was observed at 30-130 Torr total pressure of N(2) diluent. The temperature dependence of the rate constants was also studied at 213-298 K. The upper limit of the branching ratio of OIO radical formation from IO + CH(3)O(2) was estimated to be <0.1. The reaction rate constants of IO + C(2)H(5)O(2) and IO + CF(3)O(2) were determined to be (14 +/- 6) x 10(-11) and (6.3 +/- 2.7) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K, 100 Torr of N(2) diluent, respectively. The upper limit of the reaction rate constant of IO with CH(3)I was <4 x 10(-14) cm(3) molecule(-1) s(-1).

17.
J Phys Chem A ; 110(23): 7401-5, 2006 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-16759128

RESUMO

The reaction of nitrate radical with dimethyl sulfide was studied with cavity ring-down spectroscopy in 20-200 Torr of N2 diluent in the temperature range of 283-318 K. The rate constant for this reaction, k(1), is found to be temperature dependent and pressure independent: k1 = 4.5(-2.8)(+4.0) x 10(-13) exp[(310 +/- 220)/T] cm3 molecule(-1) s(-1). The uncertainties are two standard deviations from regression analyses. The present rate constants are in good agreement with those reported by Daykin and Wine (Int. J. Chem. Kinet. 1990, 22, 1083) and may be used in the atmospheric model calculation. Theoretical calculations were carried out to verify the existence of an intermediate complex.


Assuntos
Nitratos/química , Ésteres do Ácido Sulfúrico/química , Temperatura , Radicais Livres/química , Cinética , Modelos Químicos , Pressão , Fatores de Tempo
18.
J Phys Chem A ; 109(8): 1587-93, 2005 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-16833481

RESUMO

The reactions of Cl atoms with XCH2I (X = H, CH3, Cl, Br, I) have been studied using cavity ring-down spectroscopy in 25-125 Torr total pressure of N2 diluent at 250 K. Formation of the XCH2I-Cl adduct is the dominant channel in all reactions. The visible absorption spectrum of the XCH2I-Cl adduct was recorded at 405-632 nm. Absorption cross-sections at 435 nm are as follows (in units of 10(-18) cm2 molecule(-1)): 12 for CH3I, 21 for CH3CH2I, 3.7 for CH2ICl, 7.1 for CH2IBr, and 3.7 for CH2I2. Rate constants for the reaction of Cl with CH3I were determined from rise profiles of the CH3I-Cl adduct. k(Cl + CH3I) increases from (0.4 +/- 0.1) x 10(-11) at 25 Torr to (2.0 +/- 0.3) x 10(-11) cm3 molecule(-1) s(-1) at 125 Torr of N2 diluent. There is no discernible reaction of the CH3I-Cl adduct with 5-10 Torr of O2. Evidence for the formation of an adduct following the reaction of Cl atoms with CF3I and CH3Br was sought but not found. Absorption attributable to the formation of the XCH2I-Cl adduct following the reaction of Cl atoms with XCH2I (X = H, CH3, Br, I) was measured as a function of temperature over the range 250-320 K.

19.
J Phys Chem A ; 109(29): 6527-31, 2005 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-16833998

RESUMO

We have applied cavity ring-down spectroscopy to a kinetic study of the reaction of NO3 with CH3I in 20-200 Torr of N2 diluent at 298 K. The rate constant of the reaction of NO3 + CH3I was determined to be (4.1 +/- 0.2) x 10(-13) cm3 molecule(-1) s(-1) in 100 Torr of N2 diluent at 298 K and is pressure-independent. This reaction may significantly contribute to the formation of reactive iodine compounds in the atmosphere.

20.
J Chem Phys ; 121(3): 1397-404, 2004 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-15260684

RESUMO

We report the analysis of the 2g(1D) ion-pair state of I2 by perturbation-facilitated optical-optical double resonance. The present study began with the observation of the 2g(1D)-A' 3Pi(2u) emission at around 230 nm during the analysis of the ultraviolet emissions originating form the 1u(1D) ion-pair state. The identification of this new transition helped us to specify the wavelengths for detecting the 2g(1D) state by emission, and also to estimate its absolute position. The intermediate states used to observe the 2g(1D) state were the B 3Pi(0u(+))-b' 2u mixed states by the hyperfine interaction, which allowed us to combine the X 1Sigmag(+) ground state with the 2g(1D) state in the (1+1) photon excitation following the optical selection rules for one-photon transitions: 2g(1D)<--b' 2u-B 3Pi(0u(+))<--X 1Sigmag(+). Our analysis covered the 2g(1D) state in the 0< or =v< or =12 and 9< or =J< or =40 ranges. The molecular constants and Rydberg-Klein-Rees (RKR) potential of the 2g(1D) state were reported. We discussed the occurrence of the 2g(1D)-A' 3Pi(2u) emission, when exciting to the 1u(1D) v=0 state, and attributed it to the g/u mixing between the 2g(1D) and 1u(1D) states by the hyperfine interaction. The effect of the perturbation on measured line intensities and lifetimes was evident.

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