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1.
Sci Rep ; 14(1): 15294, 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38961120

RESUMO

Reliability mapping of 5G low orbit constellation network slice is an important means to ensure link network communication. The problem of state space explosion is a typical problem. The deep reinforcement learning method is introduced. Under the 5G low orbit constellation integrated network architecture based on software definition network (SDN) and network function virtualization (NFV), the resource requirements and resource constraints of the virtual network function (VNF) are comprehensively considered to build the 5G low orbit constellation network slice reliability mapping model, and the reliability mapping model parameters are trained and learned by using deep reinforcement learning, solve the problem of state space explosion in the reliability mapping process of 5G low orbit constellation network slices. In addition, node backup and link backup strategies based on importance are adopted to solve the problem that VNF/link reliability is difficult to meet in the reliability mapping process of 5G low orbit constellation network slice. The experimental results show that this method improves the network throughput, packet loss rate and intra slice traffic of 5G low orbit constellation, and can completely repair network faults within 0.3 s; For different number of 5G low orbit constellation network slicing requests, the reliability of this method remains above 98%; For SFC with different lengths, the average network delay of this method is less than 0.15 s.

2.
ACS Appl Mater Interfaces ; 16(3): 3744-3754, 2024 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-38224058

RESUMO

In the realm of organic solar cells (OSCs), the width of the depletion region at the anode interface is a critical factor that adversely impacts the open-circuit voltage (Voc) and the power conversion efficiency (PCE). To address this challenge, a novel approach involving a conjugated polyelectrolyte (CPE)-based composite, PCP-2F-Li:POM, has been developed. This composite serves as a solution-processed hole transport layer (HTL), effectively minimizing the depletion region width in high-performance OSCs. The innovative aspect of PCP-2F-Li:POM lies in its "mutual doping" mechanism. Polyoxometalate (POM) is utilized as a dopant, facilitating the formation of p-doped CPE and n-doped POM within the composite. This results in a substantial increase in doping density, nearly 2 orders of magnitude higher than that observed in unmodified CPE. Consequently, the width of depletion region is markedly reduced, shrinking from 76.4 to 6.0 nm. This reduction plays a pivotal role in enhancing hole transport via the tunneling effect. The practical impact of this development is notable. It leads to an increase in Voc from 0.84 to 0.86 V, thereby contributing significantly to an impressive PCE of 18.04% in OSCs. Moreover, the compatibility of PCP-2F-Li:POM with large-area processing techniques underscores its potential as a viable HTL material for future practical applications. Additionally, its contribution to the enhanced long-term stability of OSCs further bolsters its suitability for practical applications.

3.
ACS Nano ; 18(4): 3276-3285, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38252155

RESUMO

Although protonated polyoxometalates (POMs) are promising hole-transporting layer (HTL) materials for optoelectronic devices owing to their excellent hole collection/injection property, pH neutrality, and noncorrosiveness, POMs are seldom used as high-performance HTL materials. Herein, we designed and synthesized a series of mixed-additive POMs with pH-neutral counterions (NH4+, K+, and Na+) as HTL materials. X-ray photoelectron spectroscopy and single-crystal X-ray analyses indicated that the use of the lacunary heteropolyanion [P2W15O56]12- as an intermediate ensured successful incorporation of the counterions into the mixed-addenda POMs without causing deterioration of the POM frameworks. The hole-transporting layer performance of POM-NH4, which was characterized by a high work function and good conductivity and could be prepared using a low-cost method surpassed those of its protonated counterpart POM-4 and many classic HTL materials. An organic solar cell (OSC) modified with POM-NH4 delivered a power conversion efficiency of 18.0%, which was the highest photovoltaic efficiency achieved by POM-based OSCs to date. Moreover, an HTL material based on POM-NH4 reduced the turn-on voltage of an organic light-emitting diode from 4.2 to 3.2 V. The results of this study suggest that POMs are promising alternatives to the classic HTL materials owing to their excellent hole-collection ability, low costs, neutral nature, and high-chemical stability.

4.
Nat Chem ; 16(1): 22-27, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38182762

RESUMO

Trans-cis photoisomerization is generally described by a model in which the reaction proceeds via a common intermediate having a perpendicular conformation around the rotating bond, irrespective of from which isomer the reaction starts. Nevertheless, such an intermediate has yet to be identified unambiguously, and it is often called the 'phantom' state. Here we present the structural identification of the common, perpendicular intermediate of stilbene photoisomerization using ultrafast Raman spectroscopy. Our results reveal ultrafast birth and decay of an identical, short-lived transient that exhibits a vibrational signature characteristic of the perpendicular state upon photoexcitation of the trans and cis forms. In combination with ab initio molecular dynamics simulations, it is shown that the photoexcited trans and cis forms are funnelled off to the ground state through the same, perpendicular intermediate.

5.
Opt Express ; 30(9): 14873-14885, 2022 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-35473221

RESUMO

We present theoretically obtained photoelectron momentum distributions (PMDs) for the strong field ionization of argon in an elliptically polarized laser field at a central wavelength of 400 nm. Three different theoretical approaches, namely, a numerical solution of the time-dependent Schrödinger equation (TDSE), a nonadiabatic model, and a classical-trajectory Monte Carlo (CTMC) model are adopted in our calculations. From the TDSE calculations, it is found that the attoclock offset angle (most probable electron emission angles with respect to the minor axis of the laser's polarization ellipse) in the PMD increases with rising ATI order. While this result cannot be reproduced by the CTMC model, the nonadiabatic model achieves good agreement with the TDSE result. Analysis shows that the nonadiabatic corrections of the photoelectron initial momentum distribution (in both longitudinal and transverse directions with respect to the tunneling direction) and nonadiabatic correction of the tunneling exit are responsible for the ATI order-dependent angular shift.

6.
J Chem Phys ; 151(21): 214308, 2019 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-31822095

RESUMO

We employ few-cycle pulses to strong-field-ionize di-iodomethane (CH2I2) and femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy to investigate the subsequent ultrafast dissociative ionization and vibrational wave packet dynamics. Probing in the spectral region of the I 4d core-level transitions, the time-resolved XUV differential absorption spectra reveal the population of several electronic states of CH2I2 + by strong-field ionization. Global analysis reveals three distinct time scales for the observed dynamics: 20 ± 2 fs, 49 ± 6 fs, and 157 ± 9 fs, ascribed to relaxation of the CH2I2 + parent ion from the Franck-Condon region, dissociation of high-lying excited states of CH2I2 + to I+ (3P2), CH2I, and I2 + (2Π3/2,g), and dissociation of CH2I2 + to I (2P3/2) and CH2I+, respectively. Oscillatory features in the time-resolved XUV differential absorption spectra point to the generation of vibrational wave packets in both the residual CH2I2 and the CH2I2 + parent ion. Analysis of the oscillation frequencies and phases reveals, in the case of neutral CH2I2, C-I symmetric stretching induced by bond softening and I-C-I bending driven by a combination of bond softening and R-selective depletion. In the case of CH2I2 +, both the fundamental and first overtone frequencies of the I-C-I bending mode are observed, indicating large-amplitude I-C-I bending motion, in good agreement with results obtained from ab initio simulations of the XUV transition energy along the I-C-I bend coordinate. These results show that femtosecond XUV absorption spectroscopy is well-suited for studying ultrafast photodissociation and vibrational wave packet dynamics.

7.
J Phys Chem Lett ; 9(19): 5742-5747, 2018 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-30212632

RESUMO

Visualizing the real-time dissociation of chemical bonds represents a challenge in the study of ultrafast molecular dynamics due to the simultaneous need for sub-angstrom spatial and femtosecond temporal resolution. Here, we follow the C-I dissociation dynamics of strong-field-ionized 2-iodopropane (2-C3H7I) with femtosecond extreme ultraviolet (XUV) absorption spectroscopy. By probing the iodine 4 d core-level absorption, we resolve a continuous XUV spectral shift on the sub-100 fs time scale that accompanies the dissociation of the 2-C3H7I+ spin-orbit-excited 2 E1/2 state to yield atomic I in the 2 P3/2 state. In combination with ab initio calculations of the C-I distance-dependent XUV transition energy, we reconstruct the temporal evolution of the C-I distance from the Franck-Condon region to the asymptotic region with 10 fs and 0.1 Å resolution. The C-I bond elongation appears to couple to coherent vibrational motion along the HC(CH3)2 umbrella mode of the 2-C3H7+ fragment, whose effect on the I 4 d XUV transition even at C-I distances of 3.5 Å points to the long-range nature of XUV absorption probing. Our results suggest that femtosecond XUV absorption spectroscopy, in combination with ab initio simulations of XUV transition energies, can be used to resolve the ultrafast structural dynamics of large polyatomic molecules.

8.
J Phys Chem Lett ; 8(24): 6067-6072, 2017 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-29190098

RESUMO

Studies of ultrafast molecular dynamics induced by intense laser fields can reveal new approaches to manipulating chemical reactions in the strong-field regime. Here, we show that intense few-cycle laser pulses can induce the spin-orbit state-selective C-I dissociation of the iodomethane cation (CH3I+) in the X̃ electronic state. Irradiation of CH3I by 6 fs laser pulses with peak intensities of 1.9 × 1014 W/cm2 followed by femtosecond extreme ultraviolet probing of the iodine 4d core-level transitions reveals dissociation of the CH3I+ X̃ 2E1/2 state with a time constant of 0.76 ± 0.16 ps. By contrast, the X̃ 2E3/2 spin-orbit ground state does not exhibit any appreciable dissociation on the picosecond time scale. The observed spin-orbit state-selective dissociation of the X̃ state is rationalized in terms of the laser-induced coupling to the à state. Our results suggest that the intense-laser control of photodissociation channels can be potentially extended to spin-orbit split states.

9.
Nat Commun ; 8(1): 735, 2017 09 29.
Artigo em Inglês | MEDLINE | ID: mdl-28963448

RESUMO

Strong-field laser-molecule interaction forms much of the basis for initiating and probing ultrafast quantum dynamics. Previous studies aimed at elucidating the origins of vibrational coherences induced by intense laser fields have been confined to diatomic molecules. Furthermore, in all cases examined to date, vibrational wave packet motion is found to be induced by R-selective depletion; wave packet motion launched by bond softening, though theoretically predicted, remains hitherto unobserved. Here we employ the exquisite sensitivity of femtosecond extreme ultraviolet absorption spectroscopy to sub-picometer structural changes to observe both bond softening-induced vibrational wave packets, launched by the interaction of intense laser pulses with iodomethane, as well as multimode vibrational motion of the parent ion produced by strong-field ionization. In addition, we show that signatures of coherent vibrational motion in the time-dependent extreme ultraviolet absorption spectra directly furnish vibronic coupling strengths involving core-level transitions, from which geometrical parameters of transient core-excited states are extracted.Nuclear dynamics of polyatomic molecules involves multiple degrees of freedom and is challenging to explore. Here the authors study the internuclear distance-dependent depletion and bond-softening induced vibrational wavepacket dynamics of CH3I molecules using femtosecond XUV transient absorption spectroscopy.

10.
J Phys Chem B ; 118(6): 1510-8, 2014 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-24447185

RESUMO

Light absorption by the photoreceptor microbial rhodopsin triggers trans-cis isomerization of the retinal chromophore surrounded by seven transmembrane α-helices. Sensory rhodopsin I (SRI) is a dual functional photosensory rhodopsin both for positive and negative phototaxis in microbes. By making use of the highly stable SRI protein from Salinibacter ruber (SrSRI), the early steps in the photocycle were studied by time-resolved spectroscopic techniques. All of the temporal behaviors of the Sn←S1 absorption, ground-state bleaching, K intermediate absorption, and stimulated emission were observed in the femto- to picosecond time region by absorption spectroscopy. The primary process exhibited four dynamics similar to other microbial rhodopsins. The first dynamics (τ1 ∼ 54 fs) corresponds to the population branching process from the Franck-Condon region to the reactive (S1(r)) and nonreactive (S1(nr)) S1 states. The second dynamics (τ2 = 0.64 ps) is the isomerization process of the S1(r) state to generate the ground-state 13-cis form, and the third dynamics (τ3 = 1.8 ps) corresponds to the internal conversion of the S1(nr) state. The fourth component (τ3' = 2.5 ps) is assignable to the J-decay (K-formation). This reaction scheme was further supported by the results of fluorescence spectroscopy. To investigate the protein response(s), the spectral changes of the tryptophan bands were monitored by ultraviolet resonance Raman spectroscopy. The intensity change following the K formation in the chromophore structure (τ ∼ 17 ps) was significantly small in SrSRI as compared with other microbial rhodopsins. We also analyzed the effect(s) of Cl(-) binding on the ultrafast dynamics of SrSRI. Compared with a chloride pump Halorhodopsin, Cl(-) binding to SrSRI was less effective for the excited-state dynamics, whereas the binding altered the structural changes of tryptophan following the K-formation, which was the characteristic feature for SrSRI. On the basis of these results, a primary photoreaction scheme of SrSRI together with the role of chloride binding is proposed.


Assuntos
Bacteroidetes , Luz , Rodopsinas Sensoriais/química , Rodopsinas Sensoriais/metabolismo , Absorção , Modelos Moleculares , Conformação Proteica , Análise Espectral , Estereoisomerismo
11.
Chemphyschem ; 14(5): 936-45, 2013 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-23400968

RESUMO

Competitive bond dissociation mechanisms for bromoacetyl chloride and 2- and 3-bromopropionyl chloride following the (1) [n(O)→π*(C=O)] transition at 234-235 nm are investigated. Branching ratios for C−Br/C−Cl bond fission are found by using the (2+1) resonance-enhanced multiphoton ionization (REMPI) technique coupled with velocity ion imaging. The fragment branching ratios depend mainly on the dissociation pathways and the distances between the orbitals of Br and the C=O chromophore. C−Cl bond fission is anticipated to follow an adiabatic potential surface for a strong diabatic coupling between the n(O)π*(C=O) and np (Cl)σ*(C−Cl) bands. In contrast, C−Br bond fission is subject to much weaker coupling between n(O)π*(C=O) and np (Br)σ*(C−Br). Thus, a diabatic pathway is preferred for bromoacetyl chloride and 2-bromopropionyl chloride, which leads to excited-state products. For 3-bromopropionyl chloride, the available energy is not high enough to reach the excited-state products such that C−Br bond fission must proceed through an adiabatic pathway with severe suppression by nonadiabatic coupling. The fragment translational energies and anisotropy parameters for the three molecules are also analyzed and appropriately interpreted.

12.
J Am Chem Soc ; 133(21): 8205-10, 2011 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-21513317

RESUMO

Understanding ultrafast reactions, which proceed on a time scale of nuclear motions, requires a quantitative characterization of the structural dynamics. To track such structural changes with time, we studied a nuclear wavepacket motion in photoisomerization of a prototype cyanine dye, 1,1'-diethyl-4,4'-cyanine, by ultrafast pump-dump-probe measurements in solution. The temporal evolution of wavepacket motion was examined by monitoring the efficiency of stimulated emission dumping, which was obtained from the recovery of a ground-state bleaching signal. The dump efficiency versus pump-dump delay exhibited a finite rise time, and it became longer (97 fs → 330 fs → 390 fs) as the dump pulse was tuned to longer wavelengths (690 nm → 950 nm → 1200 nm). This result demonstrates a continuous migration of the leading edge of the wavepacket on the excited-state potential from the Franck-Condon region toward the potential minimum. A slowly decaying feature of the dump efficiency indicated a considerable broadening of the wavepacket over a wide range of the potential, which results in the spread of a population distribution on the flat S(1) potential energy surface. The rapid migration as well as broadening of the wavepacket manifests a continuous nature of the structural dynamics and provides an intuitive visualization of this ultrafast reaction. We also discussed experimental strategies to evaluate reliable dump efficiencies separately from other ultrafast processes and showed a high capability and possibility of the pump-dump-probe method for spectroscopic investigation of unexplored potential regions such as conical intersections.

13.
Chemphyschem ; 10(8): 1299-304, 2009 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-19343750

RESUMO

Photodissociation dynamics and rotational wave packet coherences of o-bromofluorobenzene are studied by femtosecond time-resolved photoelectron imaging [figure: see text]. The decay of different photoelectron rings shows the population decay of states from which the lifetimes of different states are determined. The variation of photoelectron angular distributions reflects the evolution of rotational coherences.Photodissociation dynamics and rotational wave packet coherences of o-bromofluorobenzene are studied by femtosecond time-resolved photoelectron imaging (TR-PEI) spectroscopy combined with the (1+2') resonance-enhanced multiphoton ionization (REMPI). Photoelectron kinetic energy and angular distributions indicate ionization dynamics from some Rydberg states at the (1+1') photon energy. The lifetimes of the S(1) (A') and T(2) (A') states are determined from the decay of the photoelectron signals to be 38 ps and 27 ps. The electron population decay of the two states is attributed to predissociation and tunneling dissociation. The variation of time-dependent anisotropy parameters in the first 5 ps shows the rotational wave coherences of molecule.

14.
J Chem Phys ; 130(14): 144309, 2009 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-19368447

RESUMO

Ultrafast processes of p-bromofluorobenzene are studied with femtosecond time-resolved photoelectron imaging spectroscopy. The photoelectron image revealed four photoelectron rings centered at 0.39, 0.86, 1.13, and 1.61 eV, respectively. The inner rings are more anisotropic than the outer rings. The decay traces of the different rings were recorded separately. Sharp photoelectron energy distributions and different anisotropy parameters extracted from the images indicated resonances with Rydberg states at the (1+1(')) photon energy. The quantum defect values of the four Rydberg states were determined to be 0.75, 0.52, 0.36, and approximately 0, respectively, with principal quantum number of 3. The electron dephasing mechanism of the S(1)(B(2)) state corresponds to the intersystem crossing from the S(1)(B(2)) to T(1)(B(2)) state and the predissociation of the S(1)(B(2)) state via the T(1)(B(1)) state. The lifetimes of S(1)(B(2)) and T(1)(B(2)) are determined from the decay of the photoelectron signals to be 40 and 33 ps, respectively. The variety of time-dependent anisotropy parameters in the first 5 ps shows the rotational wave coherences of p-bromofluorobenzene at the S(1)(B(2)) state.

15.
J Chem Phys ; 130(1): 014307, 2009 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-19140615

RESUMO

Velocity imaging technique combined with (2+1) resonance-enhanced multiphoton ionization (REMPI) is used to detect primary photodissociation of propionyl chloride. In one-color experiments at 235 nm, the Cl and Cl(*) fragments are produced rapidly, leading to a fraction of translational energy release of 0.37 and 0.35, anisotropy parameters of 1.1 and 0.8, and quantum yield of 0.67 and 0.33, respectively, when initial excitation of the (1)(n, pi(*))(CO) band is coupled to the (1)(n(Cl), sigma(C-Cl)(*)) repulsive configuration. The resulting propionyl radical with sufficient internal energy may undergo secondary dissociation to yield CO that is characteristic of an isotropic distribution. The REMPI spectra of the CO (0,0) and (1,1) bands are measured, giving rise to a Boltzmann rotational temperature of 1200 and 770 K, respectively, and a Boltzmann vibrational temperature of 2800 K. A minor channel of HCl elimination is not detected, probably because of predissociation in two-photon absorption at 235 nm. In two-color experiments comprising an additional 248 nm photolyzing laser, Cl and Cl(*) are produced with a fraction of translational energy release of 0.43 and 0.40 and anisotropy parameters of 1.0 and 0.6, respectively. The secondary production of CO is not observed although the internal energy partitioned in the propionyl radical is in the proximity of the dissociation barrier. In either experimental scheme, a small component appearing in the center of the Cl and Cl(*) images is proposed to stem from ground state dissociation via internal conversion.

16.
Chemphyschem ; 9(12): 1721-8, 2008 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-18624286

RESUMO

A velocity imaging technique combined with (2+1) resonance-enhanced multiphoton ionization (REMPI) is used to detect the primary Br((2)P(3/2)) fragment in the photodissociation of o-, m-, and p-dibromobenzene at 266 nm. The obtained translational energy distributions suggest that the Br fragments are produced via two dissociation channels. For o- and m-dibromobenzene, the slow channel that yields an anisotropy parameter close to zero is proposed to stem from excitation of the lowest excited singlet (pi,pi*) state followed by predissociation along a repulsive triplet (n,sigma*) state localized on the C-Br bond. The fast channel that gives rise to an anisotropy parameter of 0.53-0.73 is attributed to a bound triplet state with smaller dissociation barrier. For p-dibromobenzene, the dissociation rates are reversed, because the barrier for the bound triplet state becomes higher than the singlet-triplet crossing energy. The fractions of translational energy release are determined to be 6-8 and 29-40 % for the slow and fast channels, respectively; the quantum yields are 0.2 and 0.8, and are insensitive to the position of the substituent. The Br fragmentation from bromobenzene and bromofluorobenzenes at the same photolyzing wavelength is also compared to understand the effect of the number of halogen atoms on the phenyl ring.


Assuntos
Bromobenzenos/química , Bromo/química , Compostos de Bromo/química , Compostos de Flúor/química , Espectrometria de Massas , Fotoquímica
17.
Chemphyschem ; 9(8): 1130-6, 2008 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-18438772

RESUMO

The velocity imaging technique combined with (2+1) resonance-enhanced multiphoton ionization (REMPI) is used to detect the halogen fragments in the photodissociation of bromobenzene and iodobenzene at 266 nm. With the aid of potential energy curve calculations by Lunell (Y. J. Liu, P. Persson, S. Lunell, J. Phys. Chem. A 2004, 108, 2339-2345.), the Br fragmentation is proposed to stem from excitation of the lowest excited singlet (pi-pi*) state followed by predissociation along a repulsive triplet (n-sigma*) state. The slowed dissociation rate leads to production of the isotropic Br fragments and 93 % internal energy deposition. Only the ground state Br((2)P(3/2)) is detectable. In contrast, when iodine is substituted, the iodine effect stabilizes the repulsive states associated with the I-C6H5 bond rupture and the subsequent dissociation channels become more complicated. 84 % of the iodobenzene molecules obtained follow a direct dissociation channel, while the remaining undergo a predissociative process. Both routes result in rapid dissociation with anisotropy parameters of 0.7+/-0.2 and 0.9+/-0.2 as well as 70 % and 26 % in the fractions of translational energy deposition, respectively. The relative quantum yields of I* and I are 0.35 and 0.65 and their related photodissociation pathways are discussed in detail.

18.
J Phys Chem A ; 112(17): 3846-51, 2008 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-18363387

RESUMO

The dissociative ionization and the Coulomb explosion of CH3I irradiated by a 35 fs 800 nm laser with a laser intensity of 4 x 10(13) to 6 x 10(14) W/cm2 was studied. In a relatively weak laser field (about 10(13) W/cm2), the dissociative ionization of CH3I took place. The speed distributions of the CH3+ and I+ fragments were measured and fitted using multiple Gaussian functions. Different product channels were found for CH3+ and I+, respectively. In a strong laser field (about 10(14) W/cm2), the multiply ionized fragment ions of Iq+ (q

19.
Artigo em Inglês | MEDLINE | ID: mdl-17267280

RESUMO

The photodissociation dynamics of CH(2)Br(2) was investigated near 234 and 267 nm. A two-dimensional photofragment ion velocity imaging technique coupled with a [2+1] resonance-enhanced multiphoton (REMPI) ionization scheme was utilized to obtain the angular and translational energy distributions of the nascent Br ((2)P(3/2)) and Br* ((2)P(1/2)) atoms. The obtained translational energy distributions of Br and Br* are found consist of two components which should be come from the radical channel and secondary dissociation process, respectively. It is suggested that the symmetry reduction from C(2v) to C(s) during photodissociation invokes a non-adiabatic coupling between the 2B(1) and A(1) states. Consequently, the higher internal energy distribution of Br channel than Br* formation channel and the broader translational energy distribution of the former are presumed correlate with a variety of vibrational excitation disposal at the crossing point resulting from the larger non-adiabatic crossing from 2B(1) to A(1) state than the reverse crossing. Moreover, the measured anisotropy parameter beta indicate that fragments recoil along the Br-Br direction mostly in the photodissociation.


Assuntos
Bromo/química , Hidrocarbonetos Bromados/química , Calorimetria , Cinética , Espectrometria de Massas , Fotólise , Fótons , Espectrofotometria Ultravioleta
20.
J Chem Phys ; 125(18): 184307, 2006 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-17115752

RESUMO

The photodissociation dynamics of tert-C(4)H(9)Br and iso-C(4)H(9)Br has been studied at 234 and 265 nm using two-dimensional velocity map imaging technique. The translational energy and angular distributions have been analyzed for Br, Br(*), and tert-C(4)H(9) radical. The energy distribution of Br atom in the photodissociation of tert-C(4)H(9)Br is found to consist of two Gaussian components. The two components are correlated to two independent reaction paths on the excited potential energy surfaces: (1) the high-energy component from the prompt dissociation along the C-Br stretching mode and (2) the low-energy component from the repulsive mode along the C-Br stretching, coupled with some bending motions. For the energy distribution of Br(*) atom in the photodissociation of tert-C(4)H(9)Br, a third multiphoton dissociative ionization channel is observed at 265 nm in addition to the two energy components corresponding to channels (1) and (2). The energy distributions of Br and Br(*) atoms in the photodissociation of iso-C(4)H(9)Br can be fitted using only one Gaussian function indicating a single formation channel. Relative quantum yields for Br((2)P(32)) at 234 and 265 nm in the photodissociation of tert-C(4)H(9)Br are measured to be 0.76 and 0.65, respectively. For iso-C(4)H(9)Br, the measured value is Phi(234 nm)(Br)=0.81. The contribution of bending modes to Br and Br(*) is much more obvious in the photodissociation of tert-C(4)H(9)Br than in iso-C(4)H(9)Br.

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